Borophosphates are intermediate compounds of systems MxOy–B2O3–P2O5–(H2O) (M = main group or transition metal) which contain complex anionic structures built of interconnected trigonal–planar BO3 and / or BO4 and PO4 groups and their partially protonated species. The main objective of the present work was to synthesize, characterize and to study the properties of new selected 3d transition metal borophosphates. The selected four elements are scandium (Sc), iron (Fe), cobalt (Co) and nickel (Ni) due to their interesting contributions to borophosphate structural chemistry. The mild hydrothermal method was employed for the syntheses. During the investigation of borophosphates containing alkali–metals and scandium, the following three compounds were prepared and structurally characterized: MISc[BP2O8(OH)] (MI = K, Rb), CsSc[B2P3O11(OH)3] The anionic partial structure of MISc[BP2O8(OH)] (MI = K, Rb) consists of the well known open–branched four–membered rings of alternating borate and phosphate tetrahedra (a loop–branched hexamer with B : P = 1 : 2). The anionic partial structure of CsSc[B2P3O11(OH)3] represents the new type of oligomer containing boron in three– and four– fold coordination (B : P = 2 : 3). This is also the first time that a BO3 group is not only linked to borate species but also to a phosphate tetrahedron. This kind of oligomer was already predicted for borates but was never observed. By this, CsSc[B2P3O11(OH)3] is a special compound with regard to the structural building principles of borates and borophosphates. The significant differences in the crystal structures of MISc[BP2O8(OH)] (MI = K, Rb) and CsSc[B2P3O11(OH)3] may be due to the higher coordination number of cesium. Thermal treatment (up to 1000 ºC) of these compounds resulted in white crystalline products containing new phases with unknown crystal structures. Besides the discovery of alkali–metal scandium borophosphates, five new alkali metal scandium hydrogenphosphates were synthesized and structurally characterized: Li2Sc[(PO4)(HPO4)], MISc(HPO4)2 (MI = K, Rb, Cs, NH4) It was already predicted that open framework scandium phosphates should be isotypes of the respective indium phosphates. It was also stated that there should be a whole family of scandium hydrogenphosphates as we were able to confirm with the five novel compounds. Our systematic study reveals the structural changes of the anionic partial frameworks with increasing ionic radii of the alkali–metal ion. With respect to the M―T connections (M = six coordinated central metal atom, T = four coordinated phosphorous atom) the channel size increases from 8–membered rings in Li2Sc[(PO4)(HPO4)] to 12–membered rings in MISc(HPO4)2 (MI = K, Rb, Cs, NH4). KSc(HPO4)2 exhibits a new structure type in the family of monohydrogenphosphates with the general formula MIMIII(HPO4)2. This provides further evidence that scandium is a suitable element for the synthesis of framework structures with different channel sizes. The observation that in analogy to MISc(HPO4)2 (MI = Rb, Cs, NH4) a compound exists where the MI site is replaced by H3O+ gives rise to the hope that ion exchange properties could be of interest in this class of compounds. In addition, the possible existence of further modifications (as reported for the element–combinations RbV, NH4V, RbFe, and CsIn) shoud be investigated by thermoanalytical and X–ray methods. The extensive studies on borophosphate containing the transition metals Fe, Co, Ni together with alkaline earth–metals (Mg, Ca, Sr, Ba) led to the preparation of 13 compounds containing the combination of two different divalent M1IIM2II ions: CaM2II[BP2O7(OH)3] (M2II = Fe, Ni), BaM2II[BP2O8(OH)] (M2II = Fe, Co), SrFe[BP2O8(OH)2], CaCo(H2O)[BP2O8(OH)]•H2O, M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Fe, Co, Ni) The anionic partial structure of CaM2II[BP2O7(OH)3] (M2II = Fe, Ni) consists of a tetrahedral triple [BP2O7(OH)3]4-, built from a central (HO)2BO2 tetrahedron sharing common vertices with two (H0.5)OPO3 tetrahedra. The complex anions in the crystal structure of BaM2II[BP2O8(OH)] (M2II = Fe, Co) comprises open–branched four–membered rings, [B2P4O16(OH)2]8-, which are formed by alternating (HO)BO3 and PO4 tetrahedra sharing common corners with two additional PO4 branches. The interconnection of these complex anions with M2II coordination octahedra (M2II = Fe, Co, Ni) by sharing common corners results in overall three–dimensional frameworks which contain channels filled with the M1II ions (M1II = Ca, Ba). The anionic partial structure of SrFe[BP2O8(OH)2] is built from a central (HO)2BO2 tetrahedron sharing common vertices with two PO4 tetrahedra. Surprisingly, SrFe[BP2O8(OH)2] represents the first example in the structural chemistry of borophosphates where the charge of the anionic partial structure is balanced by a divalent and a trivalent species (MIIMIII). Although being a member of the M1IIM2II[BP2O8(OH)] family the crystal structure of CaCo(H2O)[BP2O8(OH)]•H2O is different. Interestingly, this is the first case in the borophosphate structural chemistry where dimers of cobalt coordination octahedra together with borophosphate oligomers form a (two–dimensional) layered structure. The helical borophosphates M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Fe, Co, Ni) contain one–dimensional infinite loop–branched borophosphate helices built of alternatively distorted borate and phosphate tetrahedra. Up to now, the group of compounds with 1[BP2O8]3– helical chain anions has been synthesized only in combination with different cations MIMII and MIII (MI = Li, Na, K; MII = Mg, Mn, Fe, Co, Ni, Zn; MIII = Sc, In, Fe). The systematic investigation on helical borophosphates of transition metals (Fe, Co, Ni) and alkaline–earth metals showed that it is also possible to accommodate divalent metal cations within the structure without disturbing the anionic partial structure. It was not possible to find the completely ordered structural model for the compounds M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Co) but the substructure presented shows good agreement with the ordered known helical borophosphate compounds. Interestingly, it was also possible to judge the “kind of superstructure” against the crystal morphology. Syntheses of one of the few examples of borophosphates containing layered anionic partial structures (63 net topology) containing transition metal cations (Fe, Co, Ni) was realized with 6 isotypic compounds: MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Co, Ni, Ni0.5Co0.5, Ni0.8Zn0.2, Ni0.5Mg0.5) The compounds MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Co, Ni) adopt the structure type of Mg(H2O)2[B2P2O8(OH)2]•H2O characterized by a two–dimensional borophosphate anion. Substitution on the transition metal sites was shown to be possible (Ni0.5Co0.5) realized for this structure type. With the synthesis of Ni0.8Zn0.2(H2O)2[B2P2O8(OH)2]•H2O and Ni0.5Mg0.5(H2O)2[B2P2O8(OH)2]•H2O it was also proved that magnetically diluted samples can be prepared in analogy to Mg1–x Cox(H2O)2[B2P2O8(OH)2]•H2O (x = 0.25). The thermal stability of these compounds is very similar with a slight shift to higher decomposition temperatures for the Ni0.5Mg0.5(H2O)2[B2P2O8(OH)2]•H2O. In contrast to other borophosphates such as MIMII(H2O)2[BP2O8]∙H2O and MIII(H2O)2[BP2O8]∙H2O, it is not possible to rehydrate partially dehydrated samples even though the crystal structure may suggest this property. This shows that the aqua–ligands significantly contribute to the stability of the structure. The magnetic behavior of MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Ni) corresponds well with separated 3d ions without strong magnetic interactions down to 1.8 K. Quite surprising was the remarkable change in the crystal habit that was observed during the synthesis upon addition of alkali–metal cations. Syntheses with the absence of alkali–metals lead to a change in the crystal habit by reducing of the number of faces in direction of the more simple prismatic morphology. Our research on borophosphates containing mixed transition metals led to the preparation of a borophosphate and a phosphate: FeCo(H2O)[BP3O9(OH)4], Fe1.3Co0.7[P2O7]∙2H2O The anionic partial structure of FeCo(H2O)[BP3O9(OH)4] is an open–branched tetramer built from (HO)BO3 sharing common O–corners with one (HO)PO3, one (HO)2PO2 and one PO4 group. The crystal structure is an isotype to Mg2(H2O)[BP3O9(OH)4]. Fe1.3Co0.7[P2O7]∙2H2O contains the diphosphate composed of two corner–sharing tetrahedra (isotypic to MII[X2O7]∙2H2O (MII = Mg, Mn, Co, Fe and X = P, As). However, the crystal structure of both, FeCo(H2O)[BP3O9(OH)4] and Fe1.3Co0.7[P2O7]∙2H2O, contains octahedral zigzag chains, which are interconnected by the respective tetrahedral anions. The octahedral chains in these crystal structures are closely related to the octahedral arrangements in MIIH2P2O7 (MII = Co, Ni) which exhibit a field-induced metamagnetic behavior from an antiferromagnetic state to a ferromagnetic state and to MII[BPO4(OH)2] (MII = Mn, Fe, Co) which indicate a low-dimensional antiferromagnetic correlation of the MII ions by dominant exchange interactions within the one–dimensional octahedral chain structure. Therefore, due to the similar structural features, FeCo(H2O)[BP3O9(OH)4] and Fe1.3Co0.7[P2O7]∙2H2O may exhibit interesting magnetic properties. Thermal investigation revealed that both compounds are stable until 300 ºC and transform into pyrophosphates at higher temperatures. Fe1.3Co0.7[P2O7]∙2H2O represents the first hydrated mixed divalent cation diphosphate.

The hydrothermal and solid state methods were used in the synthesis of some aluminoborophosphate compounds. The products were investigated by using XRD, IR, DTA, DSC, ICP and SEM methods. The solid state reactions have been studied in the range 700 &ndash / 1200&amp / #61616 / C. Using several hydrothermal methods a novel aluminum phosphate compound Al3-xBxP3O12 was synthesized. The crystal system was found to be tetragonal with a=17.1629 and c = 12.6084A&deg / unit cell parameters and space group is P4212 (No:90). In anorthite mineral (CaAl2Si2O8) by replacing two silicon with boron and phosphorus, a boron containing anorthite with the formula of CaAl2BPO8 was prepared. The indexed data was reported for the first time in this thesis. Its crystal system was found to be monoclinic with the following unit cell parameters and &amp / #946 / angle / a=10.0440&Aring / , b = 12.6587 &Aring / , c = 14.4332 &Aring / and &amp / #946 / = 91.55&deg / . In this study, AlPO4.xH2O was also obtained by a hydrothermal method while trying to synthesize AlBP4O13. All the prepared compounds have been investigated by IR spectroscopy and the assignment of the functional B-O and P-O groups were done.

Borophosphates are intermediate compounds of systems MxOy–B2O3–P2O5–(H2O) (M = main group or transition metal) which contain complex anionic structures built of interconnected trigonal–planar BO3 and / or BO4 and PO4 groups and their partially protonated species. The main objective of the present work was to synthesize, characterize and to study the properties of new selected 3d transition metal borophosphates. The selected four elements are scandium (Sc), iron (Fe), cobalt (Co) and nickel (Ni) due to their interesting contributions to borophosphate structural chemistry. The mild hydrothermal method was employed for the syntheses. During the investigation of borophosphates containing alkali–metals and scandium, the following three compounds were prepared and structurally characterized: MISc[BP2O8(OH)] (MI = K, Rb), CsSc[B2P3O11(OH)3] The anionic partial structure of MISc[BP2O8(OH)] (MI = K, Rb) consists of the well known open–branched four–membered rings of alternating borate and phosphate tetrahedra (a loop–branched hexamer with B : P = 1 : 2). The anionic partial structure of CsSc[B2P3O11(OH)3] represents the new type of oligomer containing boron in three– and four– fold coordination (B : P = 2 : 3). This is also the first time that a BO3 group is not only linked to borate species but also to a phosphate tetrahedron. This kind of oligomer was already predicted for borates but was never observed. By this, CsSc[B2P3O11(OH)3] is a special compound with regard to the structural building principles of borates and borophosphates. The significant differences in the crystal structures of MISc[BP2O8(OH)] (MI = K, Rb) and CsSc[B2P3O11(OH)3] may be due to the higher coordination number of cesium. Thermal treatment (up to 1000 ºC) of these compounds resulted in white crystalline products containing new phases with unknown crystal structures. Besides the discovery of alkali–metal scandium borophosphates, five new alkali metal scandium hydrogenphosphates were synthesized and structurally characterized: Li2Sc[(PO4)(HPO4)], MISc(HPO4)2 (MI = K, Rb, Cs, NH4) It was already predicted that open framework scandium phosphates should be isotypes of the respective indium phosphates. It was also stated that there should be a whole family of scandium hydrogenphosphates as we were able to confirm with the five novel compounds. Our systematic study reveals the structural changes of the anionic partial frameworks with increasing ionic radii of the alkali–metal ion. With respect to the M―T connections (M = six coordinated central metal atom, T = four coordinated phosphorous atom) the channel size increases from 8–membered rings in Li2Sc[(PO4)(HPO4)] to 12–membered rings in MISc(HPO4)2 (MI = K, Rb, Cs, NH4). KSc(HPO4)2 exhibits a new structure type in the family of monohydrogenphosphates with the general formula MIMIII(HPO4)2. This provides further evidence that scandium is a suitable element for the synthesis of framework structures with different channel sizes. The observation that in analogy to MISc(HPO4)2 (MI = Rb, Cs, NH4) a compound exists where the MI site is replaced by H3O+ gives rise to the hope that ion exchange properties could be of interest in this class of compounds. In addition, the possible existence of further modifications (as reported for the element–combinations RbV, NH4V, RbFe, and CsIn) shoud be investigated by thermoanalytical and X–ray methods. The extensive studies on borophosphate containing the transition metals Fe, Co, Ni together with alkaline earth–metals (Mg, Ca, Sr, Ba) led to the preparation of 13 compounds containing the combination of two different divalent M1IIM2II ions: CaM2II[BP2O7(OH)3] (M2II = Fe, Ni), BaM2II[BP2O8(OH)] (M2II = Fe, Co), SrFe[BP2O8(OH)2], CaCo(H2O)[BP2O8(OH)]•H2O, M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Fe, Co, Ni) The anionic partial structure of CaM2II[BP2O7(OH)3] (M2II = Fe, Ni) consists of a tetrahedral triple [BP2O7(OH)3]4-, built from a central (HO)2BO2 tetrahedron sharing common vertices with two (H0.5)OPO3 tetrahedra. The complex anions in the crystal structure of BaM2II[BP2O8(OH)] (M2II = Fe, Co) comprises open–branched four–membered rings, [B2P4O16(OH)2]8-, which are formed by alternating (HO)BO3 and PO4 tetrahedra sharing common corners with two additional PO4 branches. The interconnection of these complex anions with M2II coordination octahedra (M2II = Fe, Co, Ni) by sharing common corners results in overall three–dimensional frameworks which contain channels filled with the M1II ions (M1II = Ca, Ba). The anionic partial structure of SrFe[BP2O8(OH)2] is built from a central (HO)2BO2 tetrahedron sharing common vertices with two PO4 tetrahedra. Surprisingly, SrFe[BP2O8(OH)2] represents the first example in the structural chemistry of borophosphates where the charge of the anionic partial structure is balanced by a divalent and a trivalent species (MIIMIII). Although being a member of the M1IIM2II[BP2O8(OH)] family the crystal structure of CaCo(H2O)[BP2O8(OH)]•H2O is different. Interestingly, this is the first case in the borophosphate structural chemistry where dimers of cobalt coordination octahedra together with borophosphate oligomers form a (two–dimensional) layered structure. The helical borophosphates M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Fe, Co, Ni) contain one–dimensional infinite loop–branched borophosphate helices built of alternatively distorted borate and phosphate tetrahedra. Up to now, the group of compounds with 1[BP2O8]3– helical chain anions has been synthesized only in combination with different cations MIMII and MIII (MI = Li, Na, K; MII = Mg, Mn, Fe, Co, Ni, Zn; MIII = Sc, In, Fe). The systematic investigation on helical borophosphates of transition metals (Fe, Co, Ni) and alkaline–earth metals showed that it is also possible to accommodate divalent metal cations within the structure without disturbing the anionic partial structure. It was not possible to find the completely ordered structural model for the compounds M1II0.5M2II(H2O)2[BP2O8]•H2O (M1II0.5 = Ca, Sr, Ba; M2II = Co) but the substructure presented shows good agreement with the ordered known helical borophosphate compounds. Interestingly, it was also possible to judge the “kind of superstructure” against the crystal morphology. Syntheses of one of the few examples of borophosphates containing layered anionic partial structures (63 net topology) containing transition metal cations (Fe, Co, Ni) was realized with 6 isotypic compounds: MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Co, Ni, Ni0.5Co0.5, Ni0.8Zn0.2, Ni0.5Mg0.5) The compounds MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Co, Ni) adopt the structure type of Mg(H2O)2[B2P2O8(OH)2]•H2O characterized by a two–dimensional borophosphate anion. Substitution on the transition metal sites was shown to be possible (Ni0.5Co0.5) realized for this structure type. With the synthesis of Ni0.8Zn0.2(H2O)2[B2P2O8(OH)2]•H2O and Ni0.5Mg0.5(H2O)2[B2P2O8(OH)2]•H2O it was also proved that magnetically diluted samples can be prepared in analogy to Mg1–x Cox(H2O)2[B2P2O8(OH)2]•H2O (x = 0.25). The thermal stability of these compounds is very similar with a slight shift to higher decomposition temperatures for the Ni0.5Mg0.5(H2O)2[B2P2O8(OH)2]•H2O. In contrast to other borophosphates such as MIMII(H2O)2[BP2O8]∙H2O and MIII(H2O)2[BP2O8]∙H2O, it is not possible to rehydrate partially dehydrated samples even though the crystal structure may suggest this property. This shows that the aqua–ligands significantly contribute to the stability of the structure. The magnetic behavior of MII(H2O)2[B2P2O8(OH)2]•H2O (MII = Fe, Ni) corresponds well with separated 3d ions without strong magnetic interactions down to 1.8 K. Quite surprising was the remarkable change in the crystal habit that was observed during the synthesis upon addition of alkali–metal cations. Syntheses with the absence of alkali–metals lead to a change in the crystal habit by reducing of the number of faces in direction of the more simple prismatic morphology. Our research on borophosphates containing mixed transition metals led to the preparation of a borophosphate and a phosphate: FeCo(H2O)[BP3O9(OH)4], Fe1.3Co0.7[P2O7]∙2H2O The anionic partial structure of FeCo(H2O)[BP3O9(OH)4] is an open–branched tetramer built from (HO)BO3 sharing common O–corners with one (HO)PO3, one (HO)2PO2 and one PO4 group. The crystal structure is an isotype to Mg2(H2O)[BP3O9(OH)4]. Fe1.3Co0.7[P2O7]∙2H2O contains the diphosphate composed of two corner–sharing tetrahedra (isotypic to MII[X2O7]∙2H2O (MII = Mg, Mn, Co, Fe and X = P, As). However, the crystal structure of both, FeCo(H2O)[BP3O9(OH)4] and Fe1.3Co0.7[P2O7]∙2H2O, contains octahedral zigzag chains, which are interconnected by the respective tetrahedral anions. The octahedral chains in these crystal structures are closely related to the octahedral arrangements in MIIH2P2O7 (MII = Co, Ni) which exhibit a field-induced metamagnetic behavior from an antiferromagnetic state to a ferromagnetic state and to MII[BPO4(OH)2] (MII = Mn, Fe, Co) which indicate a low-dimensional antiferromagnetic correlation of the MII ions by dominant exchange interactions within the one–dimensional octahedral chain structure. Therefore, due to the similar structural features, FeCo(H2O)[BP3O9(OH)4] and Fe1.3Co0.7[P2O7]∙2H2O may exhibit interesting magnetic properties. Thermal investigation revealed that both compounds are stable until 300 ºC and transform into pyrophosphates at higher temperatures. Fe1.3Co0.7[P2O7]∙2H2O represents the first hydrated mixed divalent cation diphosphate.

The solid state, hydrothermal and flux methods were used for the investigation of alkaline earth and transition metal borophosphate compounds. The products and the phase relations were investigated by XRD, IR, DTA, and EDX methods. The solid state reactions of several boron compounds with different phosphating agents have been studied in the temperature range of 400-1200 oC. Hydrothermal and flux techniques were performed at 150 oC and 1200 oC, respectively. On the other hand, an attempt has been made to prepare a novel borophosphate compound MIIMIV[BPO7] (where MIV= Zr4+, Si4+, and MII= Sr2+, Ca2+) by solid state reactions and to investigate intermediate and final products. (NH4)2HPO4 and NH4H2PO4 were used as a phosphating agent. For the synthesis of these new compounds, the following reaction was predicted using the stoichiometric amount of the reactants: 2MIVO2 + 2MIICO3 + B2O3 + 2(NH4)2HPO4 &amp / #8594 / 2MIIO.MIVO2.B2O3.P2O5 + 4NH3 + 3H2O + 2CO2 (According to IUPAC formulation for the compounds composed of oxides) In the case of MIV=Zr4+ and MII=Sr2+, the formation of ZrSr[BPO7] was observed together with ZrO2 and SrBPO5. The formation of a new phase was proved by indexing the XRD pattern of the product after separating ZrO2 and SrBPO5 lines. Its crystal system was found to be orthorhombic and the unit cell parameters are a=11.85&Aring / , b=12.99 &Aring / , c=17.32 &Aring / . IR analysis shows that there is [BPO7]6- bands in the spectrum. At higher temperatures, Sr7Zr(PO4)6 was obtained. In the case of MIV=Si4+, SrBPO5 was the main product together with unreacted SiO2. At 1100 oC, Si4+ entered SrBPO5 structure and the product was indexed in orthorhombic system with a=8.9243 &Aring / , b=13.1548 &Aring / , and c=5.4036 &Aring / . Several other M:B:P ratios were tried for solid state systems. For compositions with different cations (such as Al3+, Ca2+, Na+), reactions generally pass through metal phosphates and BPO4. The X-ray diffraction powder pattern and infrared spectrum of several intermediate products obtained at different temperatures were presented and the several phase relations were investigated. The DTA and EDX analyses of some products were also reported.

Es werden neue Erkenntnisse über Borphosphat und Borophosphate der Haupt- und Nebengruppenmetalle vorgestellt. Neben Hydrothermalsynthesen und Feststoffreationen, die üblicherweise zur Synthese von Borophosphaten angewendet werden, haben insbesondere die solvothermalen Experimente mit Alkoholen bzw. Alkohol-Wasser-Mischungen zu neuen Ergebnissen geführt. Es wurden neue Borophosphate und Borat-Phosphate in den Systemen MxOy–B2O3–P2O5(–H2O) (M = K+, Rb+, Mg2+, Sc3+, Pr3+, Sm3+, In3+) dargestellt, weitere Verbindungen enthalten neben Mg2+ weitere Kationen der Haupt- und Nebengruppenmetalle (Ca, Sr, Ba, Mn, Fe, Co, Zn). Darüberhinaus gelang die Darstellung bislang unbekannter Scandium- und Lanthanphosphate(III) sowie von sauren Alkalimetall-Scandiumphosphaten(V). Aus Synthesen in Gegenwart von Ethylendiamin und Diazabizyklooktan wurden ferner zwei neue templatierte Scandiumphosphate mit porösen Gerüststrukturen erhalten. Die Kristallstrukturen aller Verbindungem wurden rötgenographisch anhand von Einkristallaufnahmen oder Pulverdaten aufgeklärt. Die Charakterisierung der Präparate erfolgte mit Röntgenpulverdiffraktometrie, EDX- und Elementaranalysen sowie durch Schwingungsspektroskopie und thermische Stabilitätsuntersuchungen. Zur Klassifizierung von (Metallo)borophosphaten wird eine Struktursystematik vorgeschlagen, welche Borophosphate und Metalloborophosphate entsprechend ihrer anionischen Teilstrukturen hierarchisch klassifiziert und in Analogie zur Terminologie der Silikate (nach Liebau) beschreibt. In Anlehnung an bestehende Konzepte für Boratminerale geht das Klassifizierungsschema dabei von einfachen Oligomeren aus. In einer struktursystematischen Übersicht wurden alle bis dato bekannten (Metallo)Borophosphate hierarchisch klassifiziert und sind in einer Übersicht vorgestellt. Beobachtete Verknüpfungsregeln und der Einfluss der Zusammensetzung B:P auf die Dimensionalität und die Verknüpfungsmuster der anionischen Teilstruktur werden diskutiert.

Es werden neue Erkenntnisse über Borphosphat und Borophosphate der Haupt- und Nebengruppenmetalle vorgestellt. Neben Hydrothermalsynthesen und Feststoffreationen, die üblicherweise zur Synthese von Borophosphaten angewendet werden, haben insbesondere die solvothermalen Experimente mit Alkoholen bzw. Alkohol-Wasser-Mischungen zu neuen Ergebnissen geführt. Es wurden neue Borophosphate und Borat-Phosphate in den Systemen MxOy–B2O3–P2O5(–H2O) (M = K+, Rb+, Mg2+, Sc3+, Pr3+, Sm3+, In3+) dargestellt, weitere Verbindungen enthalten neben Mg2+ weitere Kationen der Haupt- und Nebengruppenmetalle (Ca, Sr, Ba, Mn, Fe, Co, Zn). Darüberhinaus gelang die Darstellung bislang unbekannter Scandium- und Lanthanphosphate(III) sowie von sauren Alkalimetall-Scandiumphosphaten(V). Aus Synthesen in Gegenwart von Ethylendiamin und Diazabizyklooktan wurden ferner zwei neue templatierte Scandiumphosphate mit porösen Gerüststrukturen erhalten. Die Kristallstrukturen aller Verbindungem wurden rötgenographisch anhand von Einkristallaufnahmen oder Pulverdaten aufgeklärt. Die Charakterisierung der Präparate erfolgte mit Röntgenpulverdiffraktometrie, EDX- und Elementaranalysen sowie durch Schwingungsspektroskopie und thermische Stabilitätsuntersuchungen. Zur Klassifizierung von (Metallo)borophosphaten wird eine Struktursystematik vorgeschlagen, welche Borophosphate und Metalloborophosphate entsprechend ihrer anionischen Teilstrukturen hierarchisch klassifiziert und in Analogie zur Terminologie der Silikate (nach Liebau) beschreibt. In Anlehnung an bestehende Konzepte für Boratminerale geht das Klassifizierungsschema dabei von einfachen Oligomeren aus. In einer struktursystematischen Übersicht wurden alle bis dato bekannten (Metallo)Borophosphate hierarchisch klassifiziert und sind in einer Übersicht vorgestellt. Beobachtete Verknüpfungsregeln und der Einfluss der Zusammensetzung B:P auf die Dimensionalität und die Verknüpfungsmuster der anionischen Teilstruktur werden diskutiert.

La génération de second harmonique induite par des traitements de polarisation dans des matériaux vitreux pourrait permettre le développement de nouveaux systèmes électro-optiques compatible avec les fibres optiques de silice. Dans ce contexte, cette thèse présente les résultats obtenus par polarisation thermique des verres ((1-x) 0.95 NaPO3 + 0.05Na2B4O7)+ x Nb2O5 (x ≤ 0.5). Une non linéarité optique d'ordre deux supérieure à 4pm/V a pu être induite à la fois dans le verre massif et le verre déposé sous forme de couche mince. L'analyse du verre avant et après polarisation et notamment de la structure locale du réseau vitreux permet une meilleure approche des processus mis en jeu lors du traitement dans des verres à aussi forte concentration en sodium et donc aussi conducteurs.

The new borophosphates described here were synthesized under mild hydrothermal conditions (170 oC or 220 oC). Powder and single crystal X-ray diffraction were employed to determine and refine the crystal structures. DTA-TG methods were used to analyze the thermal stability. High temperature powder X-ray diffraction (HT-XRD) was applied to study the thermal behavior of products and identify the intermediate phase during the decomposition. Chemical analyses were performed to quantitatively determine the chemical composition. Magnetic properties of the compounds were investigated. 19F MAS NMR was used to check the number of fluorine positions in the crystal structure. The following compounds were prepared and characterized: (C2H10N2)[BPO4F2](C6H14N2){Zn[ZnB2P4O15(OH)2]¡P(C6H13N2)Cl} (zndabcocl) (C3H12N2){Mn[B2P3O12(OH)]} (DAP-Mn) and (C4H12N2){Mn[B2P3O12(OH)]} (PIP-Mn) (C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]}(C3H12N2)2{VIII2VIV3B2P8O38H8} (dapvbpo) K3[B5PO10(OH)3](C2H10N2)[BPO4F2] is the first fluorine-substituted borophosphate and the first borophosphate with crystal structure closely related to the pyroxene type structure. Unbranched zweier single chain {[BPO4F2]2?} represents a new type of borophosphate partial structure. zndabcoclrepresents the first organo-templated zincoborophosphate. The structure contains diaza-bicyclo[2.2.2]-octane (DABCO) which acts in its diprotonated form (H2DABCO)2+ as a pure template and in its monoprotonated form (HDABCO)+ as a ligand to Zn-positions at the borders of ribbons to complete structural motif. This compound is also the first example containing a quaternary Zn-tetrahedron (ZnO2NCl), and can formally be described as an adduct of (C6H14N2)Zn[ZnB2P4O15(OH)2] with diaza-bicyclo[2.2.2]octane-hydrochloride. The thermal behavior of zndabcocl has been studied by HT-XRD and DTA-TG in the temperature range 25?600 oC. The new phase occurring during the decomposition has been identified as HT-NH4[ZnBP2O8].DAP-Mnand PIP-Mn contain identical framework interconnections but difference in the shape of resulting channels, which are due to the different shape of organic templates. The crystal structures are built from the same building units: loop-branched single chains are connected via MnO6-octahedra resulting in a 3-D structure with intersecting channel systems running along [100], [011] and [01], respectively. The different shape of the template controls the shape of the channels, especially channels running along [100], resulting in dramatic shape-differences. The linear (H2DAP)2+ ions make the channels more elongated, while the cyclic (H2PIP)2+ ions give rise to more regular shaped channels. The flexibility of frameworks may be due to the more flexible coordination of Mn-atoms (octahedron and square pyramid).(C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]} is a new borophosphate with 3-D framework structure, a large size of 10-ring channel (778 ¡Ñ 867 pm2) is occupied by organic templates. The magnetic susceptibility measurements show it to exhibit antiferromagnetic susceptibility at low temperature (TN ?l 14K).dapvbpois the first mixed-valency vanadium borophosphate with a new structure type. Its structure can be considered as an ?intergrowth? of puckered vanadium(III) borophosphate layer (VIIIBPO-layer) and planar vanadium(IV) phosphate layers (VIVPO-layer) stacked and interconnected alternately along [001], which results in a new and unusual building motif. The corner sharing trimers of vanadium octahedra are observed for the first time in vanadium borophosphates. K3[B5PO10(OH)3] has a double unit cell of a twin crystal structure having the same chemical formula. The double b-axis solves the disorder problem of two oxygen positions coordinated to phosphorous. It represents a much more reasonable structure determination.

The new borophosphates described here were synthesized under mild hydrothermal conditions (170 oC or 220 oC). Powder and single crystal X-ray diffraction were employed to determine and refine the crystal structures. DTA-TG methods were used to analyze the thermal stability. High temperature powder X-ray diffraction (HT-XRD) was applied to study the thermal behavior of products and identify the intermediate phase during the decomposition. Chemical analyses were performed to quantitatively determine the chemical composition. Magnetic properties of the compounds were investigated. 19F MAS NMR was used to check the number of fluorine positions in the crystal structure. The following compounds were prepared and characterized: (C2H10N2)[BPO4F2](C6H14N2){Zn[ZnB2P4O15(OH)2]¡P(C6H13N2)Cl} (zndabcocl) (C3H12N2){Mn[B2P3O12(OH)]} (DAP-Mn) and (C4H12N2){Mn[B2P3O12(OH)]} (PIP-Mn) (C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]}(C3H12N2)2{VIII2VIV3B2P8O38H8} (dapvbpo) K3[B5PO10(OH)3](C2H10N2)[BPO4F2] is the first fluorine-substituted borophosphate and the first borophosphate with crystal structure closely related to the pyroxene type structure. Unbranched zweier single chain {[BPO4F2]2?} represents a new type of borophosphate partial structure. zndabcoclrepresents the first organo-templated zincoborophosphate. The structure contains diaza-bicyclo[2.2.2]-octane (DABCO) which acts in its diprotonated form (H2DABCO)2+ as a pure template and in its monoprotonated form (HDABCO)+ as a ligand to Zn-positions at the borders of ribbons to complete structural motif. This compound is also the first example containing a quaternary Zn-tetrahedron (ZnO2NCl), and can formally be described as an adduct of (C6H14N2)Zn[ZnB2P4O15(OH)2] with diaza-bicyclo[2.2.2]octane-hydrochloride. The thermal behavior of zndabcocl has been studied by HT-XRD and DTA-TG in the temperature range 25?600 oC. The new phase occurring during the decomposition has been identified as HT-NH4[ZnBP2O8].DAP-Mnand PIP-Mn contain identical framework interconnections but difference in the shape of resulting channels, which are due to the different shape of organic templates. The crystal structures are built from the same building units: loop-branched single chains are connected via MnO6-octahedra resulting in a 3-D structure with intersecting channel systems running along [100], [011] and [01], respectively. The different shape of the template controls the shape of the channels, especially channels running along [100], resulting in dramatic shape-differences. The linear (H2DAP)2+ ions make the channels more elongated, while the cyclic (H2PIP)2+ ions give rise to more regular shaped channels. The flexibility of frameworks may be due to the more flexible coordination of Mn-atoms (octahedron and square pyramid).(C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]} is a new borophosphate with 3-D framework structure, a large size of 10-ring channel (778 ¡Ñ 867 pm2) is occupied by organic templates. The magnetic susceptibility measurements show it to exhibit antiferromagnetic susceptibility at low temperature (TN ?l 14K).dapvbpois the first mixed-valency vanadium borophosphate with a new structure type. Its structure can be considered as an ?intergrowth? of puckered vanadium(III) borophosphate layer (VIIIBPO-layer) and planar vanadium(IV) phosphate layers (VIVPO-layer) stacked and interconnected alternately along [001], which results in a new and unusual building motif. The corner sharing trimers of vanadium octahedra are observed for the first time in vanadium borophosphates. K3[B5PO10(OH)3] has a double unit cell of a twin crystal structure having the same chemical formula. The double b-axis solves the disorder problem of two oxygen positions coordinated to phosphorous. It represents a much more reasonable structure determination.

Cette étude a porte sur la caractérisation tant physico-chimique que structurale de verres issus du système NaPO3-Na2B4O7-Ca5(PO4)3OH pouvant servir a des applications dans le domaine biomédical. Dans une première partie, les verres de composition (1-x) NaPO3-xNa2B4O7 ont été étudies. L' évolution inattendue des propriétés physicochimiques a pu être correlée a la structure caractérisée par RMN (31P MAS et 11B) et spectroscopies vibrationnelles (infrarouge et diffusion Raman). Dans une deuxième partie, l' effet d' addition de l' hydroxyapatite dans les verres borophosphates de sodium montre un renforcement de certaines propriétés (dureté et résistance a l'eau) lie a des modifications structurales du réseau vitreux. La dernière partie de ce travail a été consacré à la recherche et à la mise au point d'un procédé d'obturation de carie dentaire consistant a fondre, in situ, ces matériaux grâce au pouvoir thermique d'un laser CO2.