Temperature-dependent IR Research Articles

Estimation of vibrational spectra of Trp-cage protein from nonequilibrium metadynamics simulations

The development of methods that allow a structural interpretation of linear and nonlinear vibrational spectra is of great importance, both for spectroscopy and for optimizing force field quality. The experimentally measured signals are ensemble averages over all accessible configurations, which complicates spectral calculations. To account for this, we present a recipe for calculating vibrational amide-I spectra of proteins based on metadynamics molecular dynamics simulations. For each frame, a one-exciton Hamiltonian is set up for the backbone amide groups, in which the couplings are estimated with the transition-charge coupling model for nonnearest neighbors, and with a parametrized map of ab initio calculations that give the coupling as a function of the dihedral angles for nearest neighbors. The local-mode frequency variations due to environmental factors such as hydrogen bonds are modeled by exploiting the linear relationship between the amide C-O bond length and the amide-I frequency. The spectra are subsequently calculated while taking into account the equilibrium statistical weights of the frames that are determined using a previously published reweighting procedure. By implementing all these steps in an efficient Fortran code, the spectra can be averaged over very large amounts of structures, thereby extensively covering the phase space of proteins. Using this recipe, the spectral responses of 2.5 million frames of a metadynamics simulation of the miniprotein Trp-cage are averaged to reproduce the experimental temperature-dependent IR spectra very well. The spectral calculations provide new insight into the origin of the various spectral signatures (which are typically challenging to disentangle in the congested amide-I region), and allow for a direct structural interpretation of the experimental spectra and for validation of the molecular dynamics simulations of ensembles.

Crystal structure and spectroscopic determination of the phase transitions in methylammonium- and formamidinium bismuth iodide perovskites

Understanding of the structural properties of hybrid organic–inorganic perovskites (HOIPs) and their behavior is crucial for their use as photovoltaics and for the design and assembly of solar cells. As part of this work, a detailed study was conducted to further understand bismuth iodide perovskites, with a specific focus on the phase transitions of methylammonium and formamidinium analogs. A detailed analysis of the temperature-dependent IR spectra was also performed in order to analyze the structural changes that occur. The presence of five phases in the methylammonium bismuth iodide (MABiI) and four phases in formamidinium bismuth iodide (FABiI) were determined. An additional confirmation of the reported results was obtained from the differential scanning calorimetry. The ambiguities concerning the crystal structure of FABiI were resolved based on the results by X-ray powder diffraction (XRPD).

Tracking optical properties of VOx films to optimize polycrystalline VO2 fabrication

In-situ real-time spectroscopic ellipsometry (RTSE) measurements are performed on a growing amorphous vanadium oxide (a-VOx) film to determine the complex dielectric function (ε = ε1 + iε2) spectra, structure, and oxygen content (x) with depth during deposition. VOx with x ∼2 is annealed to produce polycrystalline VO2 and characterized by near-infrared to ultraviolet (0.75–5.9 eV) spectroscopic ellipsometry during heating and cooling from room temperature (RT) to 343 K to RT to track hysteresis effects in the semiconducting-to-metal transition (SMT). Spectra in ε are measured for as-deposited and annealed films prepared with varying deposition parameters to determine the as-deposited film x and verify the SMT. Temperature-dependent IR extended spectroscopic ellipsometry is performed from 0.06 to 0.74 eV to determine the IR ε spectra of polycrystalline VO2 across the SMT. As-deposited amorphous VOx films with x from 1.89 ≤ x ≤ 2.14 transition to polycrystalline VO2 after annealing and exhibit the SMT when heated from RT to 343 K which are verified by substantially increased ε2 magnitude at ≥343 K. By identifying x of a-VOx from ε spectra, a shortened path of qualifying a-VOx films which will crystallize to phase change VO2 is developed.

Investigation of hydrogen bonds in proton transfer complexes derived from the reaction of 2- and 4-(N,N-dimethylamino)pyridines with chloranilic acid

New complexes of 2-(N,N-dimethylamino)pyridine with chloranilic acid (2-DMAP + CLA) and 4-(N,N-dimethylamino)pyridine with chloranilic acid (4-DMAP + CLA) were synthesized and characterized by single crystal X-ray diffraction, infrared spectroscopy, thermal analysis methods and 1H, 13C and 15N NMR spectroscopy. The NMR spectroscopies were carried out in both, DMSO solution and in the solid state (CPMAS NMR). The 2-DMAP + CLA and 4-DMAP + CLA complexes crystallize in centrosymmetric P-1 and P21/c space group, respectively.In both complexes, the phenomenon of proton transfer is observed, which results in the formation of strong N+–H···O– hydrogen bonds. Thermal decompositions of 2-DMAP + CLA and 4-DMAP + CLA complexes were studied by thermogravimetric analysis. Temperature dependent IR spectra revealed that methyl groups of 4-DMAP + CLA perform fast stochastic reorientational motion at room temperature which is slowed on cooling while in 2-DMAP + CLA reonrientational motion of CH3 groups is much slower due to steric effects.

Laser induced temperature-jump time resolved IR spectroscopy of zeolites.

Combining pulsed laser heating and time-resolved infrared (TR-IR) absorption spectroscopy provides a means of initiating and studying thermally activated chemical reactions and diffusion processes in heterogeneous catalysts on timescales from nanoseconds to seconds. To this end, we investigated single pulse and burst laser heating in zeolite catalysts under realistic conditions using TR-IR spectroscopy. 1 ns, 70 μJ, 2.8 μm laser pulses from a Nd:YAG-pumped optical parametric oscillator were observed to induce temperature-jumps (T-jumps) in zeolite pellets in nanoseconds, with the sample cooling over 1-3 ms. By adopting a tightly focused beam geometry, T-jumps as large as 145 °C from the starting temperature were achieved, demonstrated through comparison of the TR-IR spectra with temperature dependent IR absorption spectra and three dimensional heat transfer modelling using realistic experimental parameters. The simulations provide a detailed understanding of the temperature distribution within the sample and its evolution over the cooling period, which we observe to be bi-exponential. These results provide foundations for determining the magnitude of a T-jump in a catalyst/adsorbate system from its absorption spectrum and physical properties, and for applying T-jump TR-IR spectroscopy to the study of reactive chemistry in heterogeneous catalysts.

Valence Tautomerism in Chromium Half-Sandwich Triarylmethylium Dyads

Valence tautomerism (VT) may occur if a molecule contains two chemically different redox-active units, which differ only slightly in their intrinsic redox potential. Herein, we present three new half-sandwich complexes [(η6-arene)Cr(CO)2L]+ with a triarylmethylium substituent appended to the π-coordinated arene and different coligands L (L = CO, P(OPh)3, PPh3, 1+–3+) at the chromium atom. Ligand substitution purposefully lowers the half-wave potential for chromium oxidation and thereby the redox potential difference towards tritylium reduction. For the PPh3-substituted complex 3+, cyclic voltammetry measurements indicate that chromium oxidation and tritylium reduction occur at (almost) the same potential. This renders the diamagnetic Cr(0)-C6H4-CAr2+ form 3+, and its paramagnetic diradical Cr(I)+•-C6H4-CAr2• valence tautomer 3+•• energetically nearly degenerate. Temperature-dependent IR spectroscopy indeed shows two pairs of carbonyl bands that are assignable to a Cr(0) and a Cr(I) species, coexisting in a T-dependent equilibrium with almost equal quantities for both at −70 °C. The diradical form with one unpaired spin at the trityl unit engages in a monomer ⇌ dimer equilibrium, which was investigated by means of quantitative EPR spectroscopy. The diradical species 1+••–3+•• were found to be highly reactive, leading to several identified reaction products, which presumably result from hydrogen atom abstraction via the trityl C atom, e.g., from the solvent.

Temperature Dependences of IR Spectral Bands of Humic Substances of Silicate-Based Soils

Temperature-dependent IR spectroscopy capable of revealing specific changes in the band intensities, positions, and shape was used to increase the information on humic substances (HS) from soils. Temperature dependences of IR spectra of HS isolated from silicate-based soils differing in the contents and nature of organic matter, chernozem and soddy podzolic soil, were investigated by attenuated total internal reflection FTIR in the mid-IR region (4000–400 cm−1) in the air within the moderate temperature range of 25–215 °C (298–488 K) with a step of 2.5 °C. The dependences of shifts in frequency (wavenumber) corresponding to band maxima and integrated band intensities were built for all major bands. Observed reversible frequency shifts upon heating and cooling can be interpreted as forming structures in the dry state. The behavior of integrated intensities of bands assigned to C–H and C–C vibrations, characteristic vibrations of polyaromatic compounds, carboxylic acids, and carboxylates were shown, and similar behavior for the same group (symmetric and antisymmetric stretches) were revealed. Differences in the temperature trends in chernozem and soddy podzolic soils due to different structures (aliphatic and aromatic) and functional groups (carboxylic and carboxylate) are shown. The different behavior of the bands corresponding to carboxylic groups and skeletal vibrations differentiates soil types with different organic matter. The temperature trends of band maximum and intensity shifts are less prone to measurement conditions and may serve as qualitative parameters characterizing the composition of soil humic substances.

New Strategy for Improvement of Interfacial Interactions between Poly(arylene sulfide sulfone) and Carbon Fiber by Grafting Polymeric Chains via Thiol-Ene Click Chemistry.

A simple and efficient strategy for enhancing the interfacial interaction in carbon fiber-reinforced poly(arylene sulfide sulfone) (CF/PASS) composites by grafting polymeric chains via thiol-ene click chemistry is reported here. Simultaneously, three thiol compounds and carbon nanotubes were grafted on CFs to explore the reaction between the CF and thiol groups. X-ray photoelectron spectroscopy, Raman spectroscopy, and normalized temperature-dependent IR spectroscopy results confirm the successful grafting of three thiol compounds, carbon nanotubes, and polymer chains. Similarly, obvious changes on the CF surface can be seen before and after modification via scanning electron microscopy, such as grafted nanotubes and polymeric resin, and the increase in the modulus gradient and interfacial thickness of CF/PASS can be clearly seen via atomic force microscopy. All the results of micro and macro tests on mechanical properties indicate that connecting low molecular weight thiol-terminated PASS (HS-LPASS) onto CFs enhances the interfacial property and mechanical performance of CF/PASS to a greater extent. The interfacial shear strength, interlaminar shear strength, and tensile strength of CF@HS-LPASS-reinforced PASS (CF@HS-LPASS/PASS) increase significantly by 38.5, 43.6, and 24.4%, respectively. All the results demonstrate that thiol-ene click reactions can be used for CF modification; furthermore, in the presence of external stress, the grafted polymeric interphase can act as a "bridge layer" to improve the stress transfer efficiency.

Elucidating NO x Surface Chemistry at the Anatase (101) Surface in TiO2 Nanoparticles.

Understanding NO x chemistry at titania nanoparticle surfaces is important for photocatalytic environmental remediation processes. We focus on this problem and put forward an experimental-computational approach based on vibrational spectroscopy grounds. Temperature-dependent IR experiments of NO x adsorption on shape-engineered nanoparticle (101) anatase surfaces are paired with power spectra obtained from Born-Oppenheimer trajectories. Then, the harmonic versus anharmonic vibrational frequencies of several adsorption scenarios are directly compared with the IR experiments. We conclude that molecules are adsorbed mainly by the N-end side and both the intermolecular interactions between adsorbed molecules and (NO)2 dimer formation are responsible for the main NO adsorption spectroscopic features. We also investigate the spectroscopy and the mechanism of formation on defective anatase surfaces of the long-lived greenhouse gas N2O.

Catalyst-free crosslinked sustainable functional silicones by supramolecular interactions

Supramolecular full silicone networks are built on the basis of siloxane polymers with low content of amino (6.4 or 9.8 mol%), and carboxyl (14.9 mo%) groups. Alternatively, the carboxyl groups involved are attached to a polyhedral silsesquioxane cage (i.e., octakis(2-carboxymethylene-thioethyl)silsesquioxane), POSS-COOH, which have also been found to play a filler role. Networks substantiated as free-standing films through the development of physical interactions between polar groups forming transverse bridges between chains were analyzed structurally by IR analysis, but also in a more original way by fluorimetric approach, and evaluated in terms of thermal, mechanical, electrical properties and their suitability as biointerfaces. It has been found that these properties are strongly dependent and can be adjusted by the content and the ratio between the two types of polar groups (-NH2 and -COOH), as well as by the substrate to which the carboxyl groups are attached (polysiloxane or POSS). Being elastomers crosslinked by supramolecular interactions, it was necessary to evaluate their reversibility, for which, temperature-dependent IR and dielectric spectroscopy studies were performed. The reflection of this reversibility in the self-healing capacity of the material in the film and solvoplasticity in solvents with different polarities and media that mimic biological fluids was highlighted supporting the sustainability of these materials obtained in the absence of any catalyst.

Experiments on the thermal activation of hydrogen release of NaBH4-sodalites characterized by IR- and MAS-NMR spectroscopy

New results on the reactions of the (BH4)-anion enclathrated in the cages of sodalites are reported. Hydrothermally synthesized NaBH4-sodalites (ǀNa8(BH4)2ǀ[SiAlO4]6) always contain hydro-sodalite type cages (ǀNa3(H2O)4ǀ[SiAlO4]3). With increasing temperature dehydration occurs. Above 250 °C a limited reaction of the residual water is going on with (BH4)-cage fillings releasing hydrogen and the appearance of certain borate specifications enclosed in the sodalite cages. The effect of a reaction of oxygen with the (BH4)-anions in the sodalite-cages at temperatures above 400 °C is also shown. The degree of (BH4)-conversion using wet and dry N2 stream is further followed by IR and MAS NMR investigations. External supply of water largely enhances the degree of reaction, e.g. at 400 °C from 16% to 44% loss of (BH4)-absorption intensity. However, 11B MAS NMR shows 8% and 22% of a conversion of (BH4)-cage fillings into new borate species in dry and wet N2 stream, respectively. These lower values are explained by a loss of B-ions via formation and evaporation of BH3 from the sodalite. Further evaluation of the 11B MAS NMR spectra could resolve the formation of (B(OH)3)-, (BO(OH)2)-, (B(OH)4)- along with unreacted (BH4)-species in the cages. 1H-MAS NMR shows a −3.8 ppm signal related to cage isolated (OH)-, which suggests an initial reaction step via (H+ + BH4−) to (BH3 + H2). The formation of (B(OH)3), however, also indicated sufficient water for a reaction of BH3 releasing further hydrogen. The formation of (BH3) could be observed in temperature dependent IR investigations at temperatures above 400 °C.

The mechanism for thermal-enhanced chaperone-like activity of α-crystallin against UV irradiation-induced aggregation of γD-crystallin

Exposure to solar UV irradiation damages γ-crystallin, leading to cataract formation via aggregation. α-Crystallin, as a small heat shock protein, efficiently suppresses this irreversible aggregation by selectively binding the denatured γ-crystallin monomer. In this study, liquid chromatography tandem mass spectrometry was used to evaluate UV-325 nm irradiation-induced photodamage of human γD-crystallin in the presence of bovine α-crystallin, atomic force microscope (AFM) and dynamic light scattering (DLS) techniques were used to detect the quaternary structure changes of the α-crystallin oligomer, and Fourier transform infrared spectroscopy and temperature-jump nanosecond time-resolved IR absorbance difference spectroscopy were used to probe the secondary structure changes of bovine α-crystallin. We find that the thermal-induced subunit dissociation of the α-crystallin oligomer involves the breaking of hydrogen bonds at the dimeric interface, leading to three different spectral components at varied temperature regions as resolved from temperature-dependent IR spectra. Under UV-325 nm irradiation, unfolded γD-crystallin binds to the dissociated α-crystallin subunit to form an αγ-complex, then follows the reassociation of the αγ-complex to the partially dissociated α-crystallin oligomer. This prevents the aggregation of denatured γD-crystallin. The formation of the γD-bound α-crystallin oligomer is further confirmed by AFM and DLS analysis, which reveals an obvious size expansion in the reassociated αγ-oligomers. In addition, UV-325 nm irradiation causes a peptide bond cleavage of γD-crystallin at Ala158 in the presence of α-crystallin. Our results suggest a very effective protection mechanism for subunits dissociated from α-crystallin oligomers against UV irradiation-induced aggregation of γD-crystallin, at the expense of a loss of a short C-terminal peptide in γD-crystallin.

Expanding the Utility of 4‐cyano‐L‐phenylalanine as a Vibrational Reporter

Unnatural amino acids (UAAs) have become useful tools for understanding protein structure and local environments. One of the most commonly used vibrational reporter UAAs to study local protein hydration environments is 4‐cyano‐L‐phenylalanine (pCNF) due to the position and sensitivity of the nitrile symmetric stretching frequency as well as the ability to efficiently incorporate this UAA site‐specifically into proteins using the Amber codon suppression methodology. Additionally, pCNF provides promise to function as a distance reporter when coupled with two‐dimensional infrared (2D IR) spectroscopy. Here, a number of superfolder green fluorescent protein (sfGFP) constructs have been generated with pCNF site‐specifically incorporated at two unique sites simultaneously. The pairs of sites were selected to permit the nitrile symmetric stretching frequency of pCNF at each site to be spectrally resolved. The temperature dependent linear IR spectra of these sfGFP constructs with two pCNF UAAs incorporated will be presented, illustrating that the nitrile groups are in different local environments. Preliminary X‐ray crystal structures of these sfGFP constructs will be presented to probe if the UAAs resulted in a structural perturbation and to determine the distance between the nitrile groups of the two pCNF UAAs in each structure. These results will serve as the basis for and calibration of employing pCNF in future 2D IR spectroscopic studies to extract the distances between these two groups based upon coupling between them.

Probing Local Protein Environments in Adenylate Kinase with 4‐Cyano‐L‐Phenylalanine

Unnatural amino acids (UAAs) containing vibrational reporters, such as nitrile, azide, and nitro groups, can be utilized to effectively probe local protein environments. Specifically, the nitrile symmetric stretching frequency of 4‐cyano‐L‐phenylalanine (pCNF) is sensitive to local protein hydration and occurs in a relatively clear region of the infrared spectrum. In addition, the magnitude of change in this vibrational frequency over a given temperature range is dependent on the local protein environment of the nitrile group of pCNF. Finally, the UAA pCNF can also be site‐specifically incorporated into proteins with high efficiency and fidelity using the Amber codon suppression methodology. Here, pCNF was incorporated into several different local protein environments in the enzyme Adenylate Kinase (AK). The successful incorporation was verified by time‐of‐flight mass spectrometry. These results in addition to the linear temperature‐dependent IR analysis of these constructs to extract the hydration state of the nitrile group of pCNF in each of these AK constructs will be presented.

Metal-Formate Framework Stiffening and Its Relevance to Phase Transition Mechanism.

In the last decade, one of the most widely examined compounds of motal-organic frameworks was undoubtedly ((CH3)2NH2)(Zn(HCOO)3), but the problem of the importance of framework dynamics in the order–disorder phase change of the mechanism has not been fully clarified. In this study, a combination of temperature-dependent dielectric, calorimetric, IR, and Raman measurements was used to study the impact of ((CH3)2NH2)(Zn(DCOO)3) formate deuteration on the phase transition mechanism in this compound. This deuteration led to the stiffening of the metal-formate framework, which in turn caused an increase in the phase transition temperature by about 5 K. Interestingly, the energetic ordering of DMA+ cations remained unchanged compared to the non-deuterated compound.

Study of thermoplastic elastomer synthesis, characterization, crystallization based on crystallizable amide segment contains conducting moiety

Thermoplastic elastomers (TPE'S) with a conducting moiety are made from Poly (tetramethylene oxide), hard segments TΦT, and sodium salt of Dimethyl-5-isothalate (DM5SIS). In the synthesis procedure, different mole percentages of the conducting moiety DM5SIS are used to see if the presence of salt affects the polymerization process and, as a result, the crystallinity of the hard segment. The synthesis of the polymer is confirmed using the 1H NMR method. The produced polymer had an inherent viscosity of 2.4–3.6 dl/g, indicating that the polymer had a high molecular weight. FT-IR techniques were used to determine the crystallinity of the hard segment in the copolymers, which revealed that the hard segment is entirely crystallised (>90%). The crystallinity is extremely reversible, according to a temperature-dependent IR investigation. The synthesised segmented copolymers DSC heating curve revealed two transitions: Tm of soft segment (SS) and melting of hard segment (HS). These materials have a very low undercooling value (about 20 °C), implying that the hard segment will crystallise quickly. The segmented copolymer that was created was clear, had a high molecular weight, and contained crystalline HS. Because the addition of a conducting moiety to the polymer chain has no effect on the polymerization process or the crystallinity of the hard segment, the polymer could be a good option for proton exchange membranes in fuel cells.

Active sites and effects of co-adsorbed H2O on isolated methanol dehydrogenation over Pt/γ-Al2O3

Dehydrogenation is the first reaction of the aqueous phase reforming (APR) mechanism of polyols, and its rate is likely affected by the environment at the active site. This study focuses on reactions of methanol on benchmark Pt/γ-Al2O3 catalysts probed by infrared spectroscopy under high vacuum. CO in linear and bridging coordination are the dominant surface species on metal sites. Pt particle sizes and reaction temperatures are varied to identify the kinetically preferred active site for methanol dehydrogenation as either lowly coordinated (edges, corners, interface) or highly coordinated (terraces) metal atoms. Interpretation of temperature-dependent IR spectra up to 450 °C show that larger Pt particles produce more CO at lower temperatures from complete methanol dehydrogenation. Similarly, time-resolved isothermal experiments at 150 °C showed equilibrium conversion occurred much faster on larger Pt particles than smaller ones. Features of evolving ν(C≡O) bands (shape, vibrational frequencies, integrals) suggest that, even on small Pt particles, CO first forms on the scarcely available terraces, or possibly in the form of islands. We have thus experimentally identified highly coordinated Pt metal as the more active site in overall methanol dehydrogenation. The electronic and chemical effects of co-adsorbed water and hydrogen on dehydrogenation activity and the CO spectra are discussed. The co-adsorption of water, an abundant APR component needed for the water-gas shift reaction, does not appear to affect methanol dehydrogenation on large Pt particles but hinders the reaction on small Pt particles as evident by limited growth in the respective ν(C≡O) bands.

Mechanism of Unusual Isosymmetric Order-Disorder Phase Transition in [Dimethylhydrazinium]Mn(HCOO)3 Hybrid Perovskite Probed by Vibrational Spectroscopy

[DMHy]Mn(HCOO)3 (DMHy+ = dimethylhydrazinium cation) is an example of an organic–inorganic hybrid adopting perovskite-like architecture with the largest organic cation used so far in the synthesis of formate-based hybrids. This compound undergoes an unusual isosymmetric phase transition at 240 K on heating. The mechanism of this phase transition has a complex nature and is mainly driven by the ordering of DMHy+ cations and accompanied by a significant distortion of the metal–formate framework in the low temperature (LT) phase. In this work, the Density Functional Theory (DFT) calculations and factor group analysis are combined with experimental temperature-dependent IR and Raman studies to unequivocally assign the observed vibrational modes and shed light on the details of the occurring structural changes. The spectroscopic data show that this first-order phase transition has a highly dynamic nature, which is a result of balanced interplay combining re-arrangement of the hydrogen bonds and ordering of DMHy+ cations. The tight confinement of organic cations forces simultaneous steric deformation of formate ions and the MnO6 octahedra.

Spectroscopic investigation of order-disorder phase transition in 4-carboxyanilinium nitrate

Co-crystal 4-carboxyanilinium nitrate (4-CAN) and its deuterated counterpart d4-CAN were studied using vibrational spectroscopy. This study is carried out to understand (i) the intra-and inter-molecular interactions in the co-crystals, 4-CAN in comparison with the parent compounds and (ii) which vibration bands of 4-CAN are affected on structural transition from monoclinic to orthorhombic phases. The Raman and infrared vibrational frequencies of 4-CAN and d4-CAN were assigned using the known frequencies of para-amino benzoic acid (PABA), partially deuterated PABA (dPABA) and HNO3. Close comparison of the spectral features of PABA and 4-CAN suggest a stronger NH…O hydrogen bond interaction and a relatively weaker hydrogen-bond interaction with the carbonyl group in 4-CAN. Temperature dependent IR study of 4-CAN across the order-disorder structural transition indicated that the vibrational bands of -NH3+ and -COOH moieties of 4-CAN are affected due to the changes taking place in hydrogen bond interaction. Present results corroborate well with the reported structural data of 4-CAN.

The mechanism of phase transitions and luminescence properties of azide perovskites

The temperature-dependent IR and Raman spectroscopy has been used to study the phase transitions in Na/K-chromium-azide frameworks with tetramethylammonium (TeMA+) cations, [(CH3)4N]2[NaCr(N3)6] and [(CH3)4N]2[KCr(N3)6], which crystallize in a perovskite-like structure. The phase transition occurring within 310–315 K in both compounds leads to a symmetry change from Pa-3 to Fm-3m and its major contributor is an order-disorder process of the organic cations followed by an adjustment of the azide bridges. The luminescence properties arise from the optically active Cr3+ ions and the studies reveal some admixture of low-symmetry component of the octahedral crystal environment of the Cr3+ sites.