Metal-Organic Frameworks (MOFs) are hybrid materials and are acknowledged as an important class of functional solid-state materials with high scientific interest in academia and industry alike. Their modular nature in terms of structural and compositional diversity, tunability, high surface area, and controlled pore size renders MOFs as the ideal candidate to address various persistent challenges pertaining to gas storage/separation, catalysis, drug delivery, and smart sensing. Through the field of reticular chemistry, targeted structures can be constructed through multiple design approaches, based on preselected building blocks prior to the assembly process. This thesis illustrates the merit of the supermolecular building layer (SBL) approach for the rational construction and discovery of highly connected and porous MOFs based on rare earth cations. Specifically, the emphasis of this study is on (i) the rational design and synthesis of 3-periodic MOFs based on SBLs pillared by ditopic ligands through post-synthetic modification (PSM) and in situ reactions. (ii) The investigation of the mixed-ligand system with different lengths and geometry of ditopic ligands on the isolation of metal clusters with distinct pore sizes. (iii) Gaining an overall insight into the exploration of different synthetic pathways that control the assembly of rare earth MOFs.

One of the historically marginalized populations in the United States (US) is the Black population. This marginalization extends into higher education, where Black students are underrepresented and continue to experience challenges, especially at Predominantly White Institutions (PWI) and in science, technology, engineering, and mathematics (STEM) programs. However, the current constitution of the Black population, including Black students in the US, is inherently culturally and ethnically diverse. The Black student population includes domestic US students and various groups of foreign-born students such as Black Sub-Saharan African (BSSA) students whose educational trajectories, outcomes, and experiences are unique based on their cultural orientations. Given the within-group differences in this population, prior research has demonstrated the need to disaggregate the experiences in research among different groups for precise research outcomes. This dissertation contributes to that effort by explicitly focusing on the lived experiences of BSSA graduate students pursuing STEM degrees at a PWI through two studies from an assets-based approach: 1) the meaning BSSA graduate students in STEM make of their lived experience with the campus climate at a PWI, using community cultural wealth as a conceptual framework; and 2) the role of family and other funds of knowledge in the educational trajectories and persistence of BSSA doctoral students pursuing STEM degrees at a PWI. I used different qualitative methodologies across both studies, including a blended case study with tenets of participatory action research in the first study in the first study and narrative analysis in the second. The results of these studies revealed that BSSA graduate students in STEM and at PWIs possessed a variety of assets that enable them to resist challenges and persist in their education. Second, the educational environments were not holistically supportive of students. Finally, there was a lack of cultural awareness and validation of students' assets and ways of knowing. The results offered implications for the BSSA graduate students in STEM in the US, scholars, practitioners at PWIs and in STEM departments who work with them, especially in creating inclusive and supportive academic environments. / Doctor of Philosophy / One of the underrepresented populations in the United States (US) is the Black population. The underrepresentation of the Black population extends into universities and colleges. Black students are underrepresented and continue to experience challenges, especially at White populated institutions (PWIs) and in science, technology, engineering, and mathematics (STEM) programs. However, the current body of the Black population, including Black students in the US, is made of many internal groups with different cultures and ethnicities. The Black student population includes domestic students from the US and other groups with international backgrounds who migrate to the US, such as Black students from Sub-Saharan Africa (BSSA), whose educational paths, performances, and experiences are different based on their cultural background. Given the internal group differences in this population, prior research has advanced the need to separately engage with the experiences among the different groups for specific research results and services for each group. This dissertation contributes to that effort by only focusing on the lived experiences of BSSA graduate students pursuing STEM degrees at a PWI through two studies on BSSA students' assets: 1) the meaning BSSA graduate students in STEM make of their lived experience with the campus climate at a PWI, using community cultural wealth as a conceptual approach; and 2) the role of family and other wealth of knowledge in the educational journeys and success of BSSA doctoral students pursuing STEM degrees at a PWI. I used different qualitative methodologies across both studies, including a blended case study with tenets of participatory action research in the first study and narrative analysis in the second. The results of these studies showed that BSSA graduate students in STEM and at PWIs possessed a variety of assets that enable them to resist challenges and persist in their education. Second, the educational environments were not entirely supportive of students. Finally, there was a lack of cultural awareness and support of students' assets and ways of learning. The results offered implications for the BSSA graduate students in STEM in the US, educators, administrators, and researchers at PWIs and in STEM departments who work with them, especially in creating inclusive and supportive academic environments.

The threat of chemical warfare agent (CWA) attacks has persisted into the 21st century due to the actions of terror groups and rogue states. Traditional filtration strategies for soldier protection rely on high surface area activated carbon, but these materials merely trap CWAs through weak physisorption. Metal-organic frameworks (MOFs) have emerged as promising materials to catalyze the degradation of CWAs into significantly less toxic byproducts. The precise synthetic control over the porosity, defect density, and chemical functionality of MOFs offer exciting potential of for use in CWA degradation as well as a wide variety of other applications. Developing a molecular-level understanding of gas-MOF interactions can allow for the rational design of MOFs optimized for CWA degradation. Our research investigated the fundamental interfacial interactions between CWA simulant vapors, specifically sulfur mustard (HD) simulants, and zirconium-based MOFs (Zr-MOFs). Utilizing a custom-built ultrahigh vacuum chamber with infrared spectroscopic and mass spectrometric capabilities, the adsorption mechanism, diffusion energetics, and diffusion kinetics of HD simulants were determined. For 2-chloroethyl ethyl sulfide (2-CEES), a widely used HD simulant, infrared spectroscopy revealed that adsorption within Zr-MOFs primarily proceeded through hydrogen bond formation between 2-CEES and the bridging hydroxyls on the secondary building unit of the MOFs. Through the study of 1-chloropentane and diethyl sulfide adsorption, we determined that 2-CEES forms hydrogen bonds through its chlorine atom likely due to geometric constraints within the MOF pore environment. Temperature-programmed desorption experiments aimed at determining desorption energetics reveal that 2-CEES remain adsorbed within the pores of the MOFs until high temperatures, but traditional methods of TPD analysis fail to accurately measure both the enthalpic and entropic interactions of 2-CEES desorption from a single adsorption site. Infrared spectroscopy was able to measure the diffusion of adsorbates within MOFs by tracking the rate of decrease in overall adsorbate concentrations at several temperatures. The results indicate that 2-CEES diffusion through the pores of the MOFs is a slow, activated process that is affected by the size of the pore windows and presence of hydrogen bonding sites. We speculate that diffusion is the rate limiting step in the desorption of HD simulants through Zr-MOFs at lower temperatures. Stochastic simulations were performed in an attempt to deconvolute TPD data in order to extract desorption parameters. Finally, a combination of vacuum-based and ambient-pressure spectroscopic techniques were employed to study the reaction between 2-CEES and an amine-functionalized MOF, UiO-66-NH2. Although the presence of water adsorbed within UiO 66 NH2 under ambient conditions may assist in the reactive adsorption of 2-CEES, the reaction proceeded under anhydrous conditions. / Doctor of Philosophy / Chemical warfare agents (CWAs) are some of the most toxic chemicals on the planet and their continued use by terror groups and rogue nations threaten the lives of both civilians and the warfighter. Our work was motivated by a class of high surface area, highly porous materials that have shown the ability to degrade CWAs, specifically mustard gas, into less harmful byproducts. By determining the adsorption mechanism (how and where mustard gas “sticks” to the material), diffusion rates (how quickly mustard gas can travel through the pores of to reach the binding sites), and desorption energies (how strongly mustard gas “sticks” to the binding sites), we can alter the structure of these materials and to efficiently trap mustard gas and render it harmless. In the research described in this dissertation, we examined these fundamental interactions for a series of molecules that mimic the structure of mustard gas. and linear alkanes within several metal-organic frameworks with varying pore size. We observed the size of the pore environment affects the orientation that a given molecule sticks to binding sites as well as how quickly these compounds diffuse through the MOF. While the majority of these studies were conducted in a low-pressure environment that eliminated the presence of gas molecules in the atmosphere, research that exposed a MOF to a mustard gas mimic in an ambient environment demonstrated that gas molecules present in the atmosphere, especially water, can greatly impact the chemical interactions between mustard gas and zirconium-based MOFs.

The work is focused on the investigation of synthesis and structure of crystalline coordination networks by combining first a row transition metal ion with one anionic and one neutral bridging ligand. In the field of crystalline coordination networks, the goal is to synthesize porous 3D crystalline coordination networks with molecular sized cavities. The materials are characterized by XRD and TGA. It is important to understand the structural topologies to develop practical applications, such as gas storage, gas separation, and catalysis. The bi- and tetra-dentate flexible imidazole ligands, 9,10-bis(imidazol-1-ylmethyl)anthracene (Chapter 2) and 1, 2, 4, 5-tetrakis(imidazol-1ylmethyl)benzene (Chapter 3), are synthesized and used as linkers to construct 1D, 2D, and 3D crystalline coordination networks with cobalt(II) or zinc(II) cations and H3BTC anions under solvothermal conditions. Two 1D chain networks, [M(HBTC²⁻)(C₂₂H₁₈N₄)(H₂O)₂]•H₂O, are constructed from M(Zn(II) or Co(II)), H₃BTC, and 9,10-bis(imidazol-1-ylmethyl)anthracene (Compound 2.1 and 2.2). These two 1D zigzag chains are linked into infinite 2D sheets by inter-chain π•••π stacking and hydrogen bonding. ⁺ Two 2D and one 3D cobalt(II) coordination networks are constructed from the tetradentate imidazole ligand and H3BTC. Compound 3.1 has a 2D corrugated sheet structure that is linked by inter-layer π•••π stacking and hydrogen bonding. Compound 3.2 has a 2D sheet structure. These sheets are interconnected by hydrogen bonds at the free acid group of the HBTC²⁻ ligand. Compound 3.3 forms a two fold interpenetrated 3D network structure. Void spaces in the structure are filled with six water molecules. Six 3D cobalt (II) coordination networks are constructed with bidentate rigid imidazole containing neutral ligands, 1,4-bis(imidazol-1-yl)benzene(L1), 1,4-bis(imidazol-1-yl)naphthalene(L2), and 9,10-bis(imidazol-1-yl)anthracene(L3), and H₂BDC or H₃BTC anion (Chapter 4). In 4.1-4.3, L1-L3 affects on degree of interpenetrations constructed with H₂BDC ligand. In 4.1 and 4.2 are interpenetrating 3D networks with no accessible void space. In 4.3, void spaces of 3D networks are filled with 2D sheets. Compounds 4.4-4.6 are prepared by different concentrations of starting materials and different solvents. In 4.4-4.6, L3 serves as a pillar building block to construct 3D networks by applying with H₃BTC ligand. The solvent exchange experiment for 4.4 is further discussed. / Ph. D.

Chapter 1: The unique chemical and biological properties of porphyrins have led to increased interest in the development of porphyrin-based materials. Metal organic frameworks (MOFs) can act as a scaffold for the immobilization of porphyrins in desired arrangements. The crystalline nature of MOFs allows for control over spatial arrangement of porphyrins and the local environment of the porphyrin molecules. This opens up the possibility of conducting systematic studies aimed at exploring structure-property relationships. Several strategies for the design and synthesis of porphyrin-based frameworks have been developed over the last two decades, such as, the pillared-layer strategy, construction of nanoscopic metal-organic polyhedrals (MOPs), post-synthetic modification, etc. These strategies provide an opportunity to engineer porphyrin-based MOFs that can target a specific application or serve as multi-functional assemblies. Porphyrin-based MOFs provide a tunable platform to perform a wide variety of functions ranging from gas adsorption, catalysis and light harvesting. The versatile nature of these frameworks can be exploited by incorporating them in multi-functional assemblies that mimic biological and enzymatic systems. Nano-thin film fabrication of porphyrin-based MOFs broadens their application range, making it possible to use them in the construction of photovoltaic and electronic devices. Chapter 2: The reaction of zirconium salts with meso-tetracarboxyphenylporphyrin (TCPP) in the presence of different modulators results in the formation of a diverse set of metal-organic frameworks (MOFs), each displaying distinct crystalline topologies. However, synthesis of phase-pure crystalline frameworks is challenging due to the concurrent formation of polymorphs. The acidity and concentration of modulator greatly influence the outcome of the MOF synthesis. By systematically varying these two parameters, selective framework formation can be achieved. In the present study, we aimed to elucidate the effect of modulator on the synthesis of zirconium-based TCPP MOFs. With the help of powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM), modulator candidates and the optimal synthetic conditions yielding phase-pure PCN-222, PCN-223 and MOF-525 were identified. 1H NMR analysis, TGA and N2 gas adsorption measurements were performed on select MOFs to gain insight into the relationship between their defectivity and modulator properties. Chapter 3: Singlet-singlet energy transfer in PCN-223(free-base), a highly stable Zr-MOF based on meso-tetrakis(4-carboxyphenyl)porphyrin was investigated, using diffuse reflectance spectroscopy, steady-state emission spectroscopy, time-correlated single photon counting (TCSPC) spectroscopy and nanosecond transient absorption spectroscopy. The effects of the surrounding media and temperature on the excited-state properties of PCN-223(fb) were explored to understand the mechanistic aspects of energy transfer. Stern-Volmer photoluminescence quenching of PCN-223(fb) suspensions was performed to extract quenching rate constants and gain insight into the efficiency of energy transfer. Chapter 4: The fourth chapter of this thesis is adapted from chapter 14 of the book "Elaboration and Applications of Metal-Organic Frameworks" authored by Jie Zhu, Shaunak Shaikh, Nicholas J Mayhall and Amanda J Morris. This chapter summarizes the fundamental principles of energy transfer in MOFs and provides an overview of energy transfer in lanthanide-Based luminescent MOFs, Ru/Os-Based MOFs, porphyrin- and metalloporphyrin-based MOF materials, and nonporphyrinic, organic chromophore-based MOFs. / Master of Science / Metal Organic frameworks (MOFs) composed of Zirconium-oxo clusters connected through meso-tetra(4-carboxyphenyl)porphyrin (TCPP) linker molecules have emerged as promising solid-state materials because of their unique structural features and diverse applications. Although these MOFs have demonstrated great potential over the years, synthesizing them in phase-pure form has proven to be very challenging as they are susceptible to polymorphism. Syntheses of these frameworks often result in phase mixtures and have poor reproducibility. To address, this issue, we conducted a systematic exploration of the synthetic parameter landscape to identify reaction conditions for the synthesis of phase-pure Zirconium-based porphyrin MOFs, and to gain deeper insights into the factors governing the formation of these MOFs. We also investigated the defectivity of pristine Zr-TCPP MOFs using a variety of techniques, including 1H NMR spectroscopy, thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and Nitrogen gas adsorption/desorption measurements. The long-term goal of this project is to use phase-pure Zr-based porphyrin MOFs as model systems to study energy transfer in three dimensional structures. To achieve this goal, we characterized the photophysical properties of PCN-223(fb) (a Zr-based porphyrin MOF) using a variety of techniques including steady-state photoluminescence spectroscopy, time-resolved photoluminescence spectroscopy, nanosecond transient absorption spectroscopy and femtosecond transient absorption spectroscopy. Understanding the mechanistic aspects of energy transfer in PCN-223(fb) can pave the way for the design of a new generation of solar energy conversion devices.

The synthesis, characterization and photophysical properties of three Zr-based Metalorganic frameworks (MOFs) assembled from 2,6-anthracenedicarboxylic acid (2,6-ADCA, 2,6- MOF) and 1,4-anthracenedicarboxylic (1,4-ADCA, 1,4-MOF), and 9,10-anthracenedicarboxylic acid (9,10-ADCA, 9,10-MOF) are described. The crystal structure of the 9,10-MOF was elucidated by synchrotron powder X-ray diffraction (PXRD) analysis and is isostructural with the well-known UiO-66 framework. The 2,6-MOFs also form highly crystalline, octahedral-shaped structures and was characterized by PXRD. Le Bail refinement of the powder pattern revealed that the 2,6-MOF also has UiO-type crystal structure. Conversely, incorporation of the 1,4-ADCA ligand results in large rod-shaped crystals. The excited-state properties of the MOFs were examined using steadstate diffuse reflectance, steady-state emission spectroscopy and time-correlated single photon counting (TCSPC) spectroscopy and are compared to those of the corresponding ligand in solution. Both the unique fluorescent properties of the ligand as well as individual framework structure, result in distinctive luminescent behavior and dictate the extent of intermolecular interactions. Specifically, the 2,6-MOF displays monomeric emission with a fluorescence lifetime (t) of 16.6 ± 1.1 and fluorescence quantum yield (Ff). On the other hand, the 1,4-MOF displays both monomeric and excimeric emission, with corresponding lifetime values of 7.5 ± 0.01 and 19.9 ± 0.1, respectively and a quantum yield of 0.002 ± 0.0001. The propensity for photon upconversion through sensitized triplet-triplet annihilation (TTA-UC) was probed in the three anthracene-based MOFs. The MOFs were surface-modified with Pd(II) mesoporphyrin IX (PdMP) as the triplet sensitizer. Upconverted emission from the 9,10-MOF was observed, with a quantum efficiency (FUC) of 0.46 % and a threshold intensity (Ith) of 142 mW/cm2 . The variation of the spacing between the anthracene units in the MOFs was found to have significant impact on TTA-UC. As a result, upconverted emission is only displayed by the 9-10-MOF. The distance between anthracene linkers in the 2,6-MOF are too large for TTA to occur, while the short distances in the 1,4-MOF inhibit upconversion through competitive excimer formation. To further explore the effects of chromophore spacing on energy transfer processes, a series of zinc-based mixed-ligand MOF were constructed from Zn(II) tetrakis(4- carboxyphenyl)porphyrin (ZnTCPP) and pyrazine, 2,2′-bipyridine (pyz) or 4,4′-bipyridyl (bpy) or 1,4-di(4-pyridyl)benzense (dpbz), comprising ZnTCPP/Zn paddlewheel layers. Across this series, the porphyrin spacing was approximately 6 Å, 11 Å and 16 Å for pyz, bpy and dpbz, respectively. The photophysical properties of the MOFs were explored using stead-state diffuse reflectance spectroscopy and steady-state and time-resolved emission spectroscopies. Florescence quenching studies examined the correlation between porphyrin spacing and efficiency of energy transfer. / Ph. D. / Metal-organic frameworks (MOFs) are crystalline materials composed of metal clusters connected by organic molecules. Their modular nature and synthetic tunability allows for rational design of MOFs with different functionalities and has afforded their application in a variety of fields including gas storage and separation, catalysis, optoelectronics, energy conversion and storage, chemical sensing and biomedicine. MOFs provide an ideal platform for studying the structure-property relationships that govern energy-transfer processes. Furthermore, efficient and long-ranging, directional energy transfer has been demonstrated in MOFs. The work presented in this dissertation focuses on MOFs with applications in solar energy conversion schemes. The design and synthesis of photoactive MOFs is described and the effects of their structure on energy-transfer processes is explored. Photovoltaic cells (PVCs) absorb sunlight and convert it into electricity. However, only photons that are high enough in energy are absorbed by the PVC, while the lower energy photons are not absorbed and therefore do not contribute to power production, resulting in decreased efficiency of the solar cell. One approach to enhancing solar cell efficiencies is to collect the lower energy photons and convert them into higher energy photons through a process called sensitized photon upconversion (UC). This process involves a molecule (sensitizer chromophore) that absorbs lower-energy photons and then transfers the absorbed energy to a second molecule (acceptor chromophore), which emits higher-energy photons. In order to understand how to optimize the efficiency of the UC process, we integrated sensitizer and acceptor chromophores into MOFs various molecular arrangements and probed UC in these materials. Close proximity and he appropriate orientation between chromophores resulted in UC from the framework. Natural photosynthetic systems contain highly ordered arrays of chromophores that efficiently absorb sunlight and funnel the energy to a reaction center. Energy-harvesting materials that mimic natural photosynthetic processes also have potential applications in solar energy conversion. Porphyrins are often used in artificial photosynthetic systems because of their similarity to chlorophyll pigments found in nature. In order to design highly efficient artificial photosynthetic systems, we first need to understand how energy transfer processes are influenced by the structure of the system. Therefore, we synthesized a series of MOFs containing Zn=porphyrin layers at varied distances and examined the effects of distance between porphyrin layers on the energy-transfer processes within the MOFs. This work provides insight into the structure-property relationships in photoactive MOFs that can serve as a guide for the rational design of light-harvesting MOFs in future studies.

In dieser Arbeit ein neues bioanalytisches Konzept untersucht, das nanoskalige Zeolith-Imidazolat-Frameworks (ZIFs) als Marker für antikörperbasierte Analysemethoden einsetzt, einschließlich Enzyme-Linked-Immunosorbent-Assay (ELISA) und Lateral Flow Immunoassay (LFIA). Der Vorteil von ZIFs als Marker gegenüber etablierten Materialien ist ihre vielseitige, einfache und kostengünstige Synthese. Dazu gehört die Möglichkeit, niedermolekulare Substanzen für zusätzliche Sensorzwecke zu verkapseln und für eine hohe Selektivität stabil an Biomakromoleküle zu konjugieren. Als modellhafter Zielanalyt von Relevanz wurden Phthalat-Acylester (PAEs) ausgewählt. Die Relevanz des Nachweises von PAEs ergibt sich aus ihren Eigenschaften als endokrin wirksame Chemikalien (EDCs) und krebserregend. In Kombination mit der Tatsache, dass PAEs aufgrund ihrer Verwendung als Weichmacher in Kindergeschirr, Spielzeug, Trinkflaschen und anderen Produkten auf Polyvinylchlorid-Basis in der Umwelt reichlich vorhanden sind, zeigt, wie wichtig der routinemäßige Nachweis von PAEs in Trinkwasser oder Lebensmitteln ist. / This work explores a new bioanalytical concept that employs nanosized Zeolite Imidazolate Frameworks (ZIFs) particles as labels for antibody-based analytical methods, including enzyme-linked immunosorbent assay (ELISA) and lateral flow immunoassay (LFIA). The advantage of ZIFs as labels over established materials is their versatile, facile, and cheap synthesis. This includes the ability to encapsulate low molecular weight substances for additional sensing purposes and for stable conjugation to biomacromolecules for high selectivity. As a model target analyte of relevance Phthalate acyl esters (PAEs) have been selected. The relevance of the detection of PAEs is due to their properties as endocrine disrupting chemicals (EDCs) and carcinogenic. Combined with PAEs being abundant on the environment because of their use as plasticizers in plastic-made tableware for children, toys, drinking bottles and other polyvinylchloride-based products, shows the importance or their routine detection of drinking water or foods being so critical.

Yes / Provision of care and support for people with dementia and family carers is complex, given variation in how dementia manifests, progresses and affects people, co-morbidities associated with ageing, as well as individual preferences, needs, and circumstances. The traditional service-led approach, where individual needs are assessed against current service provision, has been recognised as unfit to meet such complexity. As a result, people with dementia and family members often fail to receive adequate support, with needs remaining unmet. Current research lacks a conceptual framework for explaining variation in satisfaction of care needs. This work develops a conceptual framework mapped onto the care delivery process to explain variations in whether, when and why care needs of people with dementia are met and to expose individual-, service-, system-level factors that enable or hinder needs satisfaction. METHODS: Data collected through 24 in-depth interviews and two focus groups (10 participants) with people with dementia and family carers living in the North East of England (UK) were analysed thematically to develop a typology of care needs. The need most frequently reported for people with dementia (i.e. for support to go out and about) was analysed using themes stemming from the conceptual framework which combined candidacy and discrepancy theories. RESULTS: The operationalisation of the framework showed that satisfaction of the need to go out was first determined at the point of service access, affected by issues about navigation, adjudication, permeability, users' resistance to offers, users' appearance, and systems-level operating conditions, and, subsequently, at the point of service use, when factors related to service structure and care process determined (dis)satisfaction with service and, hence, further contributed to met or unmet need. CONCLUSION: The conceptual framework pinpoints causes of variations in satisfaction of care needs which can be addressed when designing interventions and service improvements. / We gratefully acknowledge financial support from the Health Foundation (grant number 1274233).

Yes / Three highly porous Zr(IV)-based metal–organic frameworks, UBMOF-8, UBMOF-9, and UBMOF-31, were synthesized by using 2,2′-diamino-4,4′-stilbenedicarboxylic acid, 4,4′-stilbenedicarboxylic acid, and combination of both linkers, respectively. The mixed-linker UBMOF-31 showed excellent hydrogen uptake of 4.9 wt% and high selectivity for adsorption of CO2 over N2 with high thermal stability and moderate water stability with permanent porosity and surface area of 2552 m2 g−1. / University of Bath; Royal Society of Chemistry; Engineering and Physical Sciences Research Council

Yes / The synthesis of metal–organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4′,4′′,4′′′-([1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6O4(OH)4(L1)2.6(L2)0.4]⋅(solvent)x, was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m2 g−1 that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers. / Financial support from EPSRC under EP/H000925, access to the HPC service ARCHER via EP/L000202. S.N. thanks the EU for a Marie Curie fellowship (PIEF-GA-2010-274952). C.M.-G. thanks the Spanish MINECO for a Ramón y Cajal Fellowship (RYC-2012-10894).