Phase Transition In Single Crystals Research Articles

Crystal Sponge Behavior in a Two-Dimensional Rare-Earth Hybrid Coordinate Polymer.

Stimuli-responsive multifunctional materials (SRMMs) have attracted tremendous attention due to their dynamic responses to external stimuli. However, it remains challenging to simultaneously achieve solvent-induced single-crystal to single-crystal (SCSC) transformation and structural phase transition after desolvation. Here, we report a two-dimensional (2D) rare-earth organic-inorganic hybrid coordinate polymer [(CH3)3NCH2Cl]2[Eu·H2O]2[CH2(SO3)2]4·2H2O (1) that exhibits a reversible SCSC transformation by changing to 2 ([(CH3)3NCH2Cl][Eu·H2O][CH2(SO3)2]2). Impressively, the SCSC transformation process couples with large changes in quantum efficiency dropped from 33.68% of 1 to 20.07% that of 2. Furthermore, polymer 2 shows an isomorphic structural phase transition associated with switching dielectric. Notably, the distance of the 2D layers shows reversible change during the two successive transition processes displaying a crystal sponge behavior. This work reveals the potential of rare-earth 2D hybrid coordination polymers in the design of multifunctional responsive materials and opens a new prospect to explore the construction of novel SRMMs.

Dicopper(II) complexes with N3,N4-bridging 1-alkyltetrazoles: Synthesis, crystal structure, magnetic and thermodynamic properties

1-R-Tetrazoles (R ​= ​Et, i-Pr, t-Bu) were found to react with copper(II) tetrafluoroborate hexahydrate and copper(II) nitrate tetrahydrate giving the complexes [Cu2L8(H2O)2]X4, where L ​= ​1-R-tetrazole, X ​= ​BF4− or NO3−. Single crystal X-ray analysis showed that the complexes comprised dinuclear cations [Cu2L8(H2O)2]4+, with six tetrazole ligands showing monodentate N4-coordination, and two ones providing N3,N4 bridges between the copper(II) cations; water molecules complete the distorted octahedral coordination of metal ions. Magnetic susceptibility measurements revealed that the copper(II) ions were very weakly antiferromagnetically coupled. Сomplex [Сu2L8(H2O)2](BF4)4 (L ​= ​1-isopropyltetrazole) was found to exhibit a temperature induced reversible single-crystal to single-crystal polymorphic phase transition. For this complex, adiabatic calorimetry was used to find the standard thermodynamic characteristics of this transition as well as the standard thermodynamic functions of the compound in the temperature range of 80–370 ​K. Additionally, mononuclear complex of the composition [CuL6](BF4)2 (L ​= ​1-ethyltetrazole) was obtained during the investigation and structurally characterized.

Unusual single crystal to single crystal phase transition of a nicotine salt monitored using temperature dependent single crystal X-ray diffraction

The organic salt (S)-nicotinium 2,6-dihydroxybenzoate undergoes reversible single crystal to single crystal phase transition at 104 K.

Thermochromism Perovskite (COOH(CH2)3NH3)2PbI4 Crystals: Single-Crystal to Single-Crystal Phase Transition and Excitation-Wavelength-Dependent Emission.

As a potential multifunctional phase transition material, the organic-inorganic hybrid perovskite has attracted extensive attention in recent years. Here, we report the single-crystal to single-crystal phase transition and excitation-wavelength-dependent emission (EDE) of layered perovskite (COOH(CH2)3NH3)2PbI4. Single-crystal X-ray diffraction indicated that the crystal structure changes from layered Ruddlesden-Popper (RP) at 302 K to "X" network composed of face-sharing and corner-sharing [PbX6]4- octahedra at 425 K. The material exhibits thermochromic change from orange to yellow at higher temperature. Considering the thermochromism of the material, we apply it for anticounterfeiting and information encryption. The material exhibits EDE properties with a fluorescence color changing from green to red upon 420 and 546 nm excitation, respectively. Time-dependent density functional theory indicated that this phenomenon is mainly related to the laser-induced crystal structural transfer. Our research shows that the (COOH(CH2)3NH3)2PbI4 crystal has a potential application for multifunctional devices.

Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals.

We study the effects of bismuth doping on the crystal structure and phase transitions in single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr3. By measuring the temperature-dependent specific heat capacity (Cp), we find that as the Bi doping increases, the phase transition assigned to the cubic to tetragonal phase boundary decreases in temperature. Furthermore, after doping we observe one phase transition between 135 and 155 K, in contrast to two transitions observed in the undoped single crystal. These results appear strikingly similar to previously reported effects of mechanical pressure on perovskite crystal structure. Using X-ray diffraction, we show that the lattice constant decreases as Bi is incorporated into the crystal, as predicted by density functional theory. We propose that bismuth substitutional doping on the lead site is dominant, resulting in BiPb+ centers that induce compressive chemical strain that alters the crystalline phase transitions.

Water Molecule-Induced Reversible Magnetic Switching in a Bis-Terpyridine Cobalt(II) Complex Exhibiting Coexistence of Spin Crossover and Orbital Transition Behaviors.

The development of molecule-based switchable materials remains an important challenge in the field of molecular science. Achievement of a structural phase transition induced by adsorption/desorption of guest molecules in spin crossover (SCO) Co(II) compounds is of significant interest because of the possibility that the spin state of the magnetic anisotropic high-spin (HS, S = 3/2) and low-spin (LS, S = 1/2) states can be switched via the induced changes in associated intermolecular interactions. In this study, we demonstrated a reversible magnetic switching associated with spin state conversion, along with a single-crystal to single-crystal (SCSC) phase transition induced by dehydration/rehydration. [Co(terpy)2](BF4)2·H2O (1·H2O; terpy = 2,2':6',2''-terpyridine) assembles in the solid state via π-π and CH-π interactions involving adjacent terpyridine cores along the ab direction to form two-dimensional (2D) layered domains. 1·H2O exhibits gradual and incomplete SCO, from fully HS to ca. 0.5 HS, and the field-induced single-molecule magnet (SMM) behavior attributed to the presence of the anisotropic partial high-spin Co(II) species. 1·H2O undergoes a SCSC transformation accompanied by a change from the tetragonal space group I41/a to P42/n via a dehydration process. Dehydrated 1 exhibits a reverse thermal hysteresis behavior (T1/2↑ = 287 K; T1/2↓ = 270 K) in the gradual SCO region from fully HS to ca. 0.5 HS, followed by an ordinary thermal hysteresis (T'1/2↑ = 195 K; T'1/2↓ = 155 K) to fully LS Co(II). A temperature-dependent single-crystal X-ray structural analysis revealed that the reverse hysteresis can be attributed to an order/disorder structural phase transition of the BF4- anions involving a symmetry breaking to yield the monoclinic space group P21/n and orbital (angular momentum) transition (LT). Both the SCSC phase transition and magnetic behavior are switchable by dehydration/rehydration processes; thus 1 again adsorbs water at room temperature to give both the original structure and its magnetic behavior.

Layered Perovskite (CH3NH3)2Pb(SCN)2I2 Single Crystals: Phase Transition and Moisture Stability.

To study stability issues of three-dimensional perovskites, there is a strategy to introduce the thiocyanate ion (SCN-) into CH3NH3PbI3 (MAPbI3) to solve these problems. Here, we report the bulk growth of layered perovskite MA2Pb(SCN)2I2 single crystals by different growth methods in an ambient atmosphere. We also investigate the structural determination and refinements, band gap, and photoluminescence of MA2Pb(SCN)2I2 single crystals. More importantly, the phase transition and stability of MA2Pb(SCN)2I2 are systematically demonstrated. MA2Pb(SCN)2I2 undergo the reversible single-crystal to single-crystal phase transition in the orthorhombic systems from the space group Pmmn (no. 59) to the space group Pmn21 (no. 31) at low temperature. Moreover, the temperature-dependent recovery behaviors of MA2Pb(SCN)2I2 single crystals, powders, and thin films at high temperature are studied in detail. Besides, the moisture stability of MA2Pb(SCN)2I2 is described when exposed to moisture condition by the experiment and theoretical calculations. It would be interesting to not only conduct a comprehensive study on the crystal structures and the phase transition processes of layered perovskites but also provide guidance for further optoelectronic applications of these perovskite materials.

Reversible, Two-Step Single-Crystal to Single-Crystal Phase Transitions between Desloratadine Forms I, II, and III

Single-crystal to single-crystal polymorphic transformations in molecular solids are relatively rare, with changes in crystal structure more commonly leading to destruction of the parent crystal. H...

Thermo/mechano-mechanically responsive cocrystals during single crystal to single crystal phase transitions

Thermo/mechano-mechanically responsive cocrystals during single crystal to single crystal phase transitions

Trigonal to Pentagonal Bipyramidal Coordination Switching in a Co(II) Single-Ion Magnet.

In molecular magnetism and single-ion magnets in particular, the observation of slow relaxation of the magnetization is intimately linked to the coordination environment of the metal center. Such systems typically have blocking temperatures well below that of liquid nitrogen, and therefore detailed magnetic characterization is usually carried out at very low temperatures. Despite this, there has been little advantage taken of ultralow temperature single-crystal X-ray diffraction techniques that could provide a full understanding of the crystal structure in the same temperature regime where slow magnetic relaxation occurs. Here, we present a systematic variable temperature single crystal X-ray diffraction study of [CoII(NO3)3(H2O)(HDABCO)] (1) {DABCO = 1,4-diazabicyclo[2.2.2]octane} conducted between 295 to 4 K. A reversible and robust disorder-to-order, single-crystal to single-crystal phase transition was identified, which accompanied a switching of the coordination geometry around the central Co(II) from 5- to 7-coordinate below 140 K. The magnetic properties were investigated, revealing slow relaxation of the magnetization arising from a large easy-plane magnetic anisotropy (+D) in the Co(II) pentagonal bipyramidal environment observed at low temperatures. This study highlights the importance of conducting thorough low temperature crystallographic studies, particularly where magnetic characterization is carried out at such low temperatures.

A non-luminescent Eu-MOF-based "turn-on" sensor towards an anthrax biomarker through single-crystal to single-crystal phase transition.

A porous NH2-MOF-76(Eu) (MOF 1) with unexpected non-luminescence was designed and synthesized. It exhibits selective fluorescence recovery for sensing dipicolinic acid (DPA), a biomarker of Bacillus anthracis. Moreover, a new europium-based MOF (MOF 2) with evident channel changes was obtained through a single-crystal to single-crystal phase transition.

Ultralong Organic Phosphorescence in the Solid State: The Case of Triphenylene Cocrystals with Halo- and Dihalo-penta/tetrafluorobenzene

The polycyclic aromatic hydrocarbon (PAH) triphenylene (TP) has been reacted with halo-pentafluorobenzene (XF5, X = Br, I) and 1,4-dihalo-tetrafluorobenzene (X2F4, X = Br, I) to yield the corresponding cocrystals TP·BrF5, TP·Br2F4, TP·IF5, and TP·I2F4 form I. These materials have been synthesized by dissolving TP into an excess of liquid or molten coformer, and single crystals have been grown via seeding chloroform solutions. They have been fully characterized by a combination of techniques including X-ray diffraction, Raman spectroscopy, and luminescence spectroscopy in the solid state. TP·I2F4 form I was found to undergo a single-crystal to single-crystal (SCSC) polymorphic phase transition induced by temperature (when cooled down to 100 K) leading to the new form TP·I2F4 form II, which is transformed back into the first structure when brought again at RT. This behavior was confirmed also by Raman spectroscopy. Upon cocrystallization and as a result of the external heavy atom effect, all crystalline mat...

An Unprecedented Stimuli-Controlled Single-Crystal Reversible Phase Transition of a Metal-Organic Framework and Its Application to a Novel Method of Guest Encapsulation.

The flexibility and unexpected dynamic behavior of a third-generation metal-organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl-based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5-benzenetricarboxylate) layers, providing a 3D porous structure (1). A phase transition of the solid can be induced to generate a new, nonporous 2D structure (2) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single-crystal-to-single-crystal transformation by single-crystal and powder X-ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl3 or supercritical CO2 induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C60 is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.

High-pressure behavior of intermediate scapolite: compressibility, structure deformation and phase transition

Scapolites are common volatile-bearing minerals in metamorphic rocks. In this study, the high-pressure behavior of an intermediate member of the scapolite solid solution series (Me47), chemical formula (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01], has been investigated up to 17.79 GPa, by means of in situ single-crystal synchrotron X-ray diffraction. The isothermal elastic behavior of the studied scapolite has been described by a III-order Birch–Murnaghan equation of state, which provided the following refined parameters: V0 = 1110.6(7) A3, $${K_{{V_0}}}$$ = 70(2) GPa ( $${\beta _{{V_0}}}$$ = 0.0143(4) GPa−1) and $${K_{{V}}^\prime}$$ = 4.8(7). The refined bulk modulus is intermediate between those previously reported for Me17 and Me68 scapolite samples, confirming that the bulk compressibility among the solid solution increases with the Na content. A discussion on the P-induced structure deformation mechanisms of tetragonal scapolite at the atomic scale is provided, along with the implications of the reported results for the modeling of scapolite stability. In addition, a single-crystal to single-crystal phase transition, which is displacive in character, has been observed toward a triclinic polymorph at 9.87 GPa. The high-pressure triclinic polymorph was found to be stable up to the highest pressure investigated.

Topological Phase Transition with Nanoscale Inhomogeneity in (Bi1- xIn x)2Se3.

Topological insulators are a class of band insulators with nontrivial topology, a result of band inversion due to the strong spin-orbit coupling. The transition between topological and normal insulator can be realized by tuning the spin-orbit coupling strength and has been observed experimentally. However, the impact of chemical disorders on the topological phase transition was not addressed in previous studies. Herein, we report a systematic scanning tunneling microscopy/spectroscopy and first-principles study of the topological phase transition in single crystals of In-doped Bi2Se3. Surprisingly, no band gap closure was observed across the transition. Furthermore, our spectroscopic-imaging results reveal that In defects are extremely effective "suppressors" of the band inversion, which leads to microscopic phase separation of topological-insulator-like and normal-insulator-like nano regions across the "transition". The observed topological electronic inhomogeneity demonstrates the significant impact of chemical disorders in topological materials, shedding new light on the fundamental understanding of topological phase transition.

Relation between Fractal Inhomogeneity and In/Nb-Arrangement in Pb(In1/2Nb1/2)O3

Relaxor ferroelectrics show substantial responses to electric fields. The key difference from normal ferroelectrics is a temperature-dependent inhomogeneous structure and its dynamics. The lead-based complex perovskite Pb(In1/2Nb1/2)O3 is an intriguing system in which the inhomogeneous structure can be controlled by thermal treatment. Herein, we report investigations of the phase transitions in single crystals of Pb(In1/2Nb1/2)O3 via changing the degree of randomness in which In and Nb occupy the B site of the ABO3 perovskite structure. We studied the dynamic properties of the structure using inelastic light scattering and the static properties using diffuse X-ray scattering. These properties depend on the degree of randomness with which the B site is occupied. When the distribution of occupied In/Nb sites is regular, the antiferroelectric phase is stabilised by a change in the collective transverse-acoustic wave, which suppresses long-range ferroelectric order and the growth of the inhomogeneous structure. However, when the B site is occupied randomly, a fractal structure grows as the temperature decreases below T*~475 K, and nanosized ferroelectric domains are produced by the percolation of self-similar and static polar nanoregions.

Temperature-Induced structural phase transformations in Cu1.50Zn0.30Te and Cu1.75Cd0.05Te single crystals

The results of studying the temperature-induced polymorphic phase transformations in Cu1.50Zn0.30Te and Cu1.75Cd0.05Te single crystals are presented. The single crystals have been investigated in the range of 290–1100 K using X-ray diffraction analysis. The temperature dependences of the unit-cell parameters, X-ray density, and coefficients of thermal expansion for each polymorphic modification of Cu1.50Zn0.30Te and Cu1.75Cd0.05Te single crystals are presented. The influence of cationic substitution (replacement of Cu2+ with Zn2+ and Cd2+ cations) on the phase-formation processes, number of polymorphic modifications, and temperature of structural phase transition in single crystals of these solid solutions is demonstrated.

High Electrical Conductivity and Conspicuous Phase Transitions in Single Crystals of K-TCNQ

This paper is to report the temperature dependent electrical conductivity of single crystals of radical ion salt (RIS) potassium-TCNQ (K-tetracyanoquino- dimethane) in a wide range of temperatures from 30 to 500 K. This RIS is quasi-one-dimensional in nature. These single crystals of K-TCNQ are grown by different methods like electrochemical, solution growth and diffusion method. Activation energy is determined for the sample in different temperature regions and found different values. More than one semiconductor to metal phase transition is observed in the studied samples during electrical measurements below and above room temperature. All the features observed in the studied samples are analyzed in the framework of their molecular structure as well as under different effects like disorder, impurity, Coulomb interaction, charge density wave (CDW), scattering and 3-D effects etc.

Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag(I) Coordination Network.

A new 3D Ag(I)-based coordination network, [Ag2(pz)(bdc)·H2O]n (1; pz = pyrazine and H2bdc = benzene-1,3-dicarboxylic acid), was constructed by one-pot assembly and structurally established by single-crystal X-ray diffraction at different temperatures. Upon cooling from 298 to 93 K, 1 undergo an interesting single-crystal to single-crystal phase transition from orthorhombic Ibca (Z = 16) to Pccn (Z = 32) at around 148 K. Both phases show a rare 2-fold-interpenetrated 4-connected lvt network but incorporate different [Ag2(COO)2] dimeric secondary building units. It is worth mentioning that complex 1 shows red- and blue-shifted luminescences in the 290-170 and 140-80 K temperature ranges, respectively. The variable-temperature single-crystal X-ray crystallographic studies suggest that the argentophilic interactions and rigidity of the structure dominated the luminescence chromism trends at the respective temperature ranges. Upon being mechanically ground, 1 exhibits a slight mechanoluminescence red shift from 589 to 604 nm at 298 K.

A temperature-induced order–disorder phase transition in a 4-substituted 4,2′:6′,4′′-terpyridine

Crystals of 4'-(isoquinolin-4-yl)-4,2':6',4''-terpyridine (iqtp), C24H16N4, grown from an ethanol solution, undergo a reversible first-order single-crystal to single-crystal phase transition at Tc in the range 273-275 K, from a disordered higher-temperature phase [form (I)] in the space group P21/c, with one single molecule in the asymmetric unit, to an ordered lower-temperature one [form (II)] in the space group P21/n, with two independent molecules in the asymmetric unit. There is a group-subgroup relationship linking (I)-(II), due to cell doubling and the disappearance of a number of symmetry operations. In addition to X-ray diffraction, the transition has been monitored by Raman spectroscopy and differential scanning calorimetry, the latter disclosing an enthalpy change of 0.72 (6) kJ mol(-1). Variations of the unit-cell parameters with temperature between 170 and 293 K are presented. The evolution of diffraction spots in the vicinity of the transition temperature shows the coexistence of both phases, confirming the first-order character of the transition. Structural details of both phases are analyzed and intermolecular interactions compared in order to investigate the mechanism of the phase transition. A three-dimensional Hirshfeld surface analysis was performed to corroborate the significant changes in the intermolecular features.