A Highly Electrostrictive Salt Cocrystal and the Piezoelectric Nanogenerator Application of Its 3D-Printed Polymer Composite.

Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CH3C6H4CH(CH3)NH2][CH3C6H4CH(CH3)NH3][PF6] ((p-TEA)(p-TEAH)·PF6) crystallizing in the polar monoclinic C2 space group. The asymmetry in (p-TEA)(p-TEAH)·PF6 was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF6- anion and the consequent formation of salt cocrystal. The ferroelectric properties of (p-TEA)(p-TEAH)·PF6 were confirmed through P-E loop measurements. Piezoresponse force microscopy (PFM) enabled the visualization of its domain structure with characteristic "butterfly" and hysteresis loops associated with ferro- and piezoelectric properties. Notably, (p-TEA)(p-TEAH)·PF6 exhibits a large electrostrictive coefficient (Q33) value of 2.02 m4 C-2, higher than those found for ceramic-based materials and comparable to that of polyvinylidene difluoride. Furthermore, the composite films of (p-TEA)(p-TEAH)·PF6 with polycaprolactone (PCL) polymer and its gyroid-shaped 3D-printed composite scaled-up device, 3DP-Gy, were prepared and evaluated for piezoelectric energy-harvesting functionality. A high output voltage of 22.8 V and a power density of 118.5 µW cm-3 have been recorded for the 3DP-Gy device. Remarkably, no loss in voltage outputs was observed for the (p-TEA)(p-TEAH)·PF6 devices even after exposure to 99% relative humidity, showcasing their utility under extremely humid conditions.

Ferroelectric Organic-Inorganic Hybrid Ammonium Halogenobismuthate(III) for Piezoelectric Energy Harvesting.

Halogenobismuthate(III) compounds are of recent interest because of their low toxicity and distinct electrical properties. The utility of these materials as ferroelectrics for piezoelectric energy harvesters is still in its early stages. Herein, we report a hybrid ammonium halogenobismuthate(III) [BPBrDMA]2·[BiBr5], crystallizing in a ferroelectrically active polar noncentrosymmetric Pna21 space group. Its noncentrosymmetric structure was confirmed by the detection of the second harmonic generation response. The ferroelectric P-E hysteresis loop measurements on the thin film sample of [BPBrDMA]2·[BiBr5] gave a saturation polarization (Ps) of 5.72 µC cm-2. The piezoresponse force microscopy analysis confirmed its ferroelectric and piezoelectric nature, showing characteristic domain structures and signature hysteresis and butterfly loops. The piezoelectric energy harvesting attributes of [BPBrDMA]2·[BiBr5] were further probed on its polylactic acid (PLA) composites. The 15 wt % [BPBrDMA]2·[BiBr5]-PLA polymer composite resulted in a high output voltage of 26.2 V and power density of 15.47 µW cm-2. The energy harvested from this device was further utilized for charging a 10 µF capacitor within 3 min.

Revisiting a (001)-oriented layered lead chloride templated by 1,2,4-triazolium: structural phase transitions, lattice dynamics and broadband photoluminescence.

This study revisits a (001)-oriented layered lead chloride templated by 1,2,4-triazolium, Tz2PbCl4, which recently has been an object of intense research but still suffers from gaps in characterization. Indeed, the divergent reports on the crystal structures of Tz2PbCl4 at various temperatures, devoid of independent verification of chiral phases through second harmonic generation (SHG), have led to an unresolved debate regarding the existence of a low-temperature phase transition (PT) and the noncentrosymmetric nature of the low-temperature phase. Now, by combining differential scanning calorimetry, single-crystal X-ray diffraction, dielectric, as well as linear and nonlinear optical spectroscopies on Tz2PbCl4, we reveal a sequence of reversible PTs at T1 = 361 K (phase I-II), T2 = 339 K (phase II-III), and T3 = 280 K (phase III-IV). No SHG activity could be registered for any of the four crystal phases, as checked by wide-temperature range SHG screening, supporting their centrosymmetry. The dipole relaxation processes indicate a decrease in activation energy with increasing temperature, from 0.60, 0.38, to 0.24 eV observed for phase IV (space group P21/c), phase III (Pnma), and phase II (Cmcm), respectively. This change is interpreted as a result of the diminishing strength of H-bonds as the system transforms from phase IV to III and subsequently to II. The weaker H-bonds facilitate the reorientation of Tz+ cations in the presence of an external electric field. The photoluminescence spectra of Tz2PbCl4 reveal an intriguing interplay of narrow and broadband emission, linked respectively to free excitons and excitons trapped on defects. Notably, as the temperature decreases from 300 K to 16 K, both the emission bands exhibit distinctive blue and red shifts, indicative of increased in-plane octahedral distortion. This dynamic behaviour transforms the photoluminescence of Tz2PbCl4 from greenish-blue at 300 K to yellowish-green at 13 K, enriching our understanding of 2D lead halide perovskites and highlighting the optoelectronic potential of Tz2PbCl4.

A Chiral B-N Adduct as a New Frontier in Ferroelectrics and Piezoelectric Energy Harvesting.

Within the burgeoning field of electronic materials, B-N Lewis acid-base pairs, distinguished by their partial charge distribution across boron and nitrogen centers, represent an underexplored class with significant potential. These materials exhibit inherent dipoles and are excellent candidates for ferroelectricity. However, the challenge lies in achieving the optimal combination of hard-soft acid-base pairs to yield B-N adducts with stable dipoles. Herein, we present an enantiomeric pair of B-N adducts [R/SC6H5CH(CH3)NH2BF3] (R/SMBA-BF3) crystallizing in the polar monoclinic P21 space group. The ferroelectric measurements on RMBA-BF3 gave a rectangular P-E hysteresis loop with a remnant polarization of 7.65 µC cm-2, a value that aligns with the polarization derived from the extensive density-functional theory computations. The PFM studies on the drop-casted film of RMBA-BF3 further corroborate the existence of ferroelectric domains, displaying characteristic amplitude-bias butterfly and phase-bias hysteresis loops. The piezoelectric nature of the RMBA-BF3 was confirmed by its direct piezoelectric coefficient (d33) value of 3.5 pC N-1 for its pellet. The piezoelectric energy harvesting applications on the sandwich devices fabricated from the as-made crystals of RMBA-BF3 gave an open circuit voltage (VPP) of 6.2 V. This work thus underscores the untapped potential of B-N adducts in the field of piezoelectric energy harvesting.

Polymorphism and Red Photoluminescence Emission from 5s2 Electron Pairs of Sb(III) in a New One-Dimensional Organic-Inorganic Hybrid Based on Methylhydrazine: MHy2SbI5.

We explore the crystal structure and luminescent properties of a new 1D organic-inorganic hybrid, MHy2SbI5, based on methylhydrazine. The compound reveals the red photoluminescence (PL) originating from the 5s2 electron pairs of Sb(III) as well as complex structural behavior. MHy2SbI5 crystalizes in two polymorphic forms (I and II) with distinct thermal properties and structural characteristics. Polymorph I adopts the acentric P212121 chiral space group confirmed by SHG, and, despite a thermally activated disorder of MHy, does not show any phase transitions, while polymorph II undergoes reversible low-temperature phase transition and high-temperature reconstructive transformation to polymorph I. The crystal structures of both forms consist of 1D perovskite zig-zag chains of corner-sharing SbI6 octahedra. The intriguing phase transition behavior of II is associated with the unstable arrangement of the [SbI5]2-∞ chains in the structure. The energy band gap (Eg) values, estimated based on the UV-Vis absorption spectra, indicate that both polymorphs have band gaps, with Eg values of 2.01 eV for polymorph I and 2.12 eV for polymorph II.

Phase Transitions, Dielectric Response, and Nonlinear Optical Properties of Aziridinium Lead Halide Perovskites.

Hybrid organic-inorganic lead halide perovskites are promising candidates for next-generation solar cells, light-emitting diodes, photodetectors, and lasers. The structural, dynamic, and phase-transition properties play a key role in the performance of these materials. In this work, we use a multitechnique experimental (thermal, X-ray diffraction, Raman scattering, dielectric, nonlinear optical) and theoretical (machine-learning force field) approach to map the phase diagrams and obtain information on molecular dynamics and mechanism of the structural phase transitions in novel 3D AZRPbX3 perovskites (AZR = aziridinium; X = Cl, Br, I). Our work reveals that all perovskites undergo order-disorder phase transitions at low temperatures, which significantly affect the structural, dielectric, phonon, and nonlinear optical properties of these compounds. The desirable cubic phases of AZRPbX3 remain stable at lower temperatures (132, 145, and 162 K for I, Br, and Cl) compared to the methylammonium and formamidinium analogues. Similar to other 3D-connected hybrid perovskites, the dielectric response reveals a rather high dielectric permittivity, an important feature for defect tolerance. We further show that AZRPbBr3 and AZRPbI3 exhibit strong nonlinear optical absorption. The high two-photon brightness of AZRPbI3 emission stands out among lead perovskites emitting in the near-infrared region.

Design and Piezoelectric Energy Harvesting Properties of a Ferroelectric Cyclophosphazene Salt.

Cyclophosphazenes offer a robust and easily modifiable platform for a diverse range of functional systems that have found applications in a wide variety of areas. Herein, for the first time, it reports an organophosphazene-based supramolecular ferroelectric [(PhCH2 NH)6 P3 N3 Me]I, [PMe]I. The compound crystallizes in the polar space group Pc and its thin-film sample exhibits remnant polarization of 5 µC cm-2 . Vector piezoresponse force microscopy (PFM) measurements indicated the presence of multiaxial polarization. Subsequently, flexible composites of [PMe]I are fabricated for piezoelectric energy harvesting applications using thermoplastic polyurethane (TPU) as the matrix. The highest open-circuit voltages of 13.7 V and the maximum power density of 34.60 µW cm-2 are recorded for the poled 20 wt.% [PMe]I/TPU device. To understand the molecular origins of the high performance of [PMe]I-based mechanical energy harvesting devices, piezoelectric charge tensor values are obtained from DFT calculations of the single crystal structure. These indicate that the mechanical stress-induced distortions in the [PMe]I crystals are facilitated by the high flexibility of the layered supramolecular assembly.

Progressive Structural Complexity in Ferroelectric 1,2,4-Triazolium Hexabromoantimonate(III): Interplay of "Order-Disorder" and "Displacive" Contributions to the Structural Phase Transitions.

Halobismuthates(III) and haloantimonates(III) with the R3MX6 chemical composition create a new and broadly unexplored class of ferroelectric compounds. In this paper, we report the haloantimonate(III) ferroelectric comprising an aromatic (1,2,4-triazolium) cation, i.e., (C2N3H4)3[SbBr6] (TBA). Temperature-resolved structural and spectroscopic studies indicate that TBA undergoes two solid-solid phase transitions between tetragonal [P42/m (I)] and monoclinic [P21/n (II) and P21 (III)] phases. TBA experiences a paraelectric-ferroelectric phase transition at 271/268 K (II-III) driven by "order-disorder" and "displacive" molecular mechanisms. The ferroelectric properties of phase III have been confirmed by hysteresis loop measurement, and additionally, the acentric order has been further supported by second-harmonic generation measurements. Insight into the molecular origins of the ferroelectric polarization was provided by periodic ab initio calculations using the Berry phase approach at the density functional theory (DFT-D3) method level employed for calculations of spontaneous polarization.

3D-printed polymer composite devices based on a ferroelectric chiral ammonium salt for high-performance piezoelectric energy harvesting.

Three-dimensional printing (3DP) is an emerging technology to fabricate complex architectures, necessary to realize state-of-the-art flexible and wearable electronic devices. In this regard, top-performing devices containing organic ferro- and piezoelectric compounds are desired to circumvent significant shortcomings of conventional piezoceramics, e.g. toxicity and high-temperature device processibility. Herein, we report on a 3D-printed composite of a chiral ferroelectric organic salt {[Me3CCH(Me)NH3][BF4]} (1) with a biodegradable polycaprolactone (PCL) polymer that serves as a highly efficient piezoelectric nanogenerator (PENG). The ferroelectric property of 1 originates from its polar tetragonal space group P42, verified by P-E loop measurements. The ferroelectric domain characteristics of 1 were further probed by piezoresponse force microscopy (PFM), which gave characteristic 'butterfly' and hysteresis loops. The PFM amplitude vs. drive voltage measurements gave a relatively high magnitude of the converse piezoelectric coefficient for 1. PCL polymer composites with various weight percentages (wt%) of 1 were prepared and subjected to piezoelectric energy harvesting tests, which gave a maximum open-circuit voltage of 36.2 V and a power density of 48.1 µW cm-2 for the 10 wt% 1-PCL champion device. Furthermore, a gyroid-shaped 3D-printed 10 wt% 1-PCL composite was fabricated to test its practical utility, which gave an excellent output voltage of 41 V and a power density of 56.8 µW cm-2. These studies promise the potential of simple organic compounds for building PENG devices using advanced manufacturing technologies.

Visualization of domain structure and piezoelectric energy harvesting in a ferroelectric metal-ligand cage.

The ferroelectric behaviour of an octahedral cage [[Ni6(H2O)12(TPTA)8]·(NO3)12·36H2O] (1) exhibiting high remnant polarization of 25.31 µC cm-2 is discovered. For the first time, clear domain structures and the characteristic electromechanical responses are demonstrated using piezoresponsive force microscopy for a thin film of 1. Owing to its mechanical energy conversion capability, polymer composites of 1 were employed as efficient piezoelectric nanogenerators.

A Ferroelectric Aminophosphonium Cyanoferrate with a Large Electrostrictive Coefficient as a Piezoelectric Nanogenerator.

Hybrid materials possessing piezo- and ferroelectric properties emerge as excellent alternatives to conventional piezoceramics due to their merits of facile synthesis, lightweight nature, ease of fabrication and mechanical flexibility. Inspired by the structural stability of aminophosphonium compounds, here we report the first A3 BX6 type cyanometallate [Ph2 (i PrNH)2 P]3 [Fe(CN)6 ] (1), which shows a ferroelectric saturation polarization (Ps ) of 3.71 µC cm-2 . Compound 1 exhibits a high electrostrictive coefficient (Q33 ) of 0.73 m4  C-2 , far exceeding those of piezoceramics (0.034-0.096 m4  C-2 ). Piezoresponse force microscopy (PFM) analysis demonstrates the polarization switching and domain structure of 1 further confirming its ferroelectric nature. Furthermore, thermoplastic polyurethane (TPU) polymer composite films of 1 were prepared and employed as piezoelectric nanogenerators. Notably, the 15 wt % 1-TPU device gave a maximum output voltage of 13.57 V and a power density of 6.03 µW cm-2 .

Exploring the Isoreticular Continuum between Phosphonate- and Phosphinate-Based Metal-Organic Frameworks.

The rational design of metal-organic frameworks (MOFs) is one of the driving forces behind the great success that this class of materials is experiencing. The so-called isoreticular approach is a key design tool, very often used to tune the size, steric properties, and additional functional groups of the linker used. In this work, we go one step further and show that even linkers with two different coordinating groups, namely, phosphonate and phosphinate, can form isoreticular MOFs. This effectively bridges the gap between MOFs utilizing phosphinate and phosphonate coordinating groups. Using a novel bifunctional ligand, 4-[hydroxy(methyl)phosphoryl]phenylphosphonic acid [H3PPP(Me)], we were able to prepare ICR-12, a MOF isoreticular to already published MOFs containing bisphosphinate linkers (e.g., ICR-4). An isostructural MOF ICR-13 was also successfully prepared using 1,4-benzenediphosphonic acid. We envisage that this strategy can be used to further enlarge the pool of MOFs.

[Methylhydrazinium]2PbCl4, a Two-Dimensional Perovskite with Polar and Modulated Phases.

Two-dimensional (2D) lead halide perovskites are a family of materials at the heart of solar cell, light-emitting diode, and photodetector technologies. This perspective leads to a number of synthetic efforts toward materials of this class, including those with prescribed polar architectures. The methylhydrazinium (MHy+) cation was recently presumed to have an unusual capacity to generate non-centrosymmetric perovskite phases, despite its intrinsically nonchiral structure. Here, we witness this effect once again in the case of the Ruddlesden-Popper perovskite phase of formula MHy2PbCl4. MHy2PbCl4 features three temperature-dependent crystal phases, with two first-order phase transitions at T1 = 338.2 K (331.8 K) and T2 = 224.0 K (205.2 K) observed in the heating (cooling) modes, respectively. Observed transitions involve a transformation from high-temperature orthorhombic phase I, with the centrosymmetric space group Pmmn, through the room-temperature modulated phase II, with the average structure being isostructural to I, to the low-temperature monoclinic phase III, with non-centrosymmetric space group P21. The intermediate phase II is a rare example of a modulated structure in 2D perovskites, with Pmmn(00γ)s00 superspace symmetry and modulation vector q ≅ 0.25c*. MHy2PbCl4 beats the previous record of MHy2PbBr4 in terms of the shortest inorganic interlayer distance in 2D perovskites (8.79 Šat 350 K vs 8.66 Šat 295 K, respectively). The characteristics of phase transitions are explored with differential scanning calorimetry, dielectric, and Raman spectroscopies. The non-centrosymmetry of phase III is confirmed with second harmonic generation (SHG) measurements, and polarity is demonstrated by the pyroelectric effect. MHy2PbCl4 also exhibits thermochromism, with the photoluminescence (PL) color changing from purplish-blue at 80 K to bluish-green at 230 K. The demonstration of polar characteristics for one more member of the methylhydrazinium perovskites settles a debate about whether this approach can present value for the crystal engineering of acentric solids similar to that which was recently adopted by a so-called fluorine substitution effect.

Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides.

Hybrid organic-inorganic lead halide perovskites have emerged as promising materials for various applications, including solar cells, light-emitting devices, dielectrics, and optical switches. In this work, we report the synthesis, crystal structures, and linear and nonlinear optical as well as dielectric properties of three imidazolium lead bromides, IMPbBr3, IM2PbBr4, and IM3PbBr5 (IM+ = imidazolium). We show that these compounds exhibit three distinct structure types. IMPbBr3 crystallizes in the 4H-hexagonal perovskite structure with face- and corner-shared PbBr6 octahedra (space group P63/mmc at 295 K), IM2PbBr4 adopts a one-dimensional (1D) double-chain structure with edge-shared octahedra (space group P1̅ at 295 K), while IM3PbBr5 crystallizes in the 1D single-chain structure with corner-shared PbBr6 octahedra (space group P1̅ at 295 K). All compounds exhibit two structural phase transitions, and the lowest temperature phases of IMPbBr3 and IM3PbBr5 are noncentrosymmetric (space groups Pna21 at 190 K and P1 at 100 K, respectively), as confirmed by measurements of second-harmonic generation (SHG) activity. X-ray diffraction and thermal and Raman studies demonstrate that the phase transitions feature an order-disorder mechanism. The only exception is the isostructural P1̅ to P1̅ phase transition at 141 K in IM2PbBr4, which is of a displacive type. Dielectric studies reveal that IMPbBr3 is a switchable dielectric material, whereas IM3PbBr5 is an improper ferroelectric. All compounds exhibit broadband, highly shifted Stokes emissions. Features of these emissions, i.e., band gap and excitonic absorption, are discussed in relation to the different structures of each composition.

Structural, magnetic and photoluminescence properties of new hybrid hypophosphites: discovery of the first noncentrosymmetric and two cobalt-based members.

Hybrid organic-inorganic perovskites comprising hypophosphite ligands are emerging functional materials exhibiting magnetic, photoluminescence, negative thermal expansion and negative linear compressibility behaviours. This work reports five novel hypophosphite perovskites, [A]M(H2POO)3 (A = pyrrolidinium (PYR+), guanidinium (GUA+) and imidazolium (IM+); M = Cd2+ and Co2+). [GUA]Cd(H2POO)3, [IM]Cd(H2POO)3, [GUA]Co(H2POO)3 and [IM]Co(H2POO)3 belong to the centrosymmetric trigonal R3̄c, monoclinic P21/c, monoclinic I2/m, and orthorhombic Pbca space groups, respectively, while [PYR]Cd(H2POO)3 crystallizes in the noncentrosymmetric orthorhombic space group Aea2. The polar order of PYR+ cations was confirmed by observation of moderate second harmonic generation (SHG) activity. Magnetic studies reveal that [GUA]Co(H2POO)3 and [IM]Co(H2POO)3 are weak ferromagnets with the ordering temperatures higher compared to their manganese analogues. Upon ultraviolet excitation, the cadmium counterparts exhibit purplish-blue emissions at low temperatures, which decrease on heating. Analysis of the photoluminescence data reveals that the emission quenching decreases with decreasing distortion of the cadmium-hypophosphite framework. Discovery of the new hypophosphites exhibiting magnetic or polar order and photoluminescence properties shows that hypophosphite perovskites offer a promising platform for generating new functional materials, including those that are light emitting, ferroelectric and multiferroic.

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation.

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)3 P]3 [Bi2 Br9 ] (MTPBB) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 µC cm-2 . Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d33 ) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 µW cm-2 at an optimal load of 4 MΩ. Moreover, the potential of MTPBB-based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.

Ferroelectricity and Piezoelectric Energy Harvesting of Hybrid A2BX4-Type Halogenocuprates Stabilized by Phosphonium Cations.

Perovskite-structured compounds containing organic cations and inorganic anions have gained prominence as materials for next-generation electronic and energy devices. Hybrid materials possessing ferro- and piezoelectric properties are in recent focus for mechanical energy harvesting (nanogenerator) applications. Here, we report the ferroelectric behavior of A2BX4-type halogenocuprate materials supported by heteroleptic phosphonium cations. These lead-free discrete Cu(II) halides [Ph3MeP]2[CuCl4] (1) and [Ph3MeP]2[CuBr4] (2) exhibit a remnant polarization (P r) of 17.16 and 26.02 µC cm-2, respectively, at room temperature. Furthermore, flexible polymer films were prepared with various weight percentage (wt %) compositions of 1 in thermoplastic polyurethane (TPU) and studied for mechanical energy harvesting applications. A highest peak-to-peak voltage output of 25 V and power density of 14.1 µW cm-2 were obtained for the optimal 15 wt % 1-TPU composite film. The obtained output voltages were utilized for charging a 100 µF electrolytic capacitor that reaches its maximum charging point within 30 s with sizable stored energies and accumulated charges.

A Flexible Energy Harvester from an Organic Ferroelectric Ammonium Salt.

Organic ferroelectrics due to their low cost, easy preparation, light weight, high flexibility and phase stability are gaining tremendous attention in the field of portable electronics. In this work, we report the synthesis, structure and ferroelectric behavior of a two-component ammonium salt 2, containing a bulky [Bn(4-BrBn)NMe2 ]+ (Bn=benzyl and 4-BrBn=4-bromobenzyl) cation and tetrahedral (BF4 )- anion. The structural analysis revealed the presence of rich non-classical C-H⋅⋅⋅F and C-H⋅⋅⋅Br interactions in this molecule that were quantified by Hirshfeld surface analysis. The polarization (P) vs. electric field (E) hysteresis loop measurements on 2 gave a remnant polarization (Pr ) of 14.4 µC cm-2 at room temperature. Flexible polymer composites with various (5, 10, 15 and 20) weight percentages (wt%) of 2 in thermoplastic polyurethane (TPU) were prepared and tested for mechanical energy harvesting applications. A notable peak-to-peak output voltage of 20 V, maximum current density of 1.1 µA cm-2 and power density of 21.1 µW cm-2 were recorded for the 15 wt% 2-TPU composite device. Furthermore, the voltage output generated from this device was utilized to rapidly charge a 100 µF capacitor, with stored energies and measured charges of 156 µJ and 121.6 µC, respectively.

Benzyltrimethylammonium cadmium dicyanamide with polar order in multiple phases and prospects for linear and nonlinear optical temperature sensing.

Coordination polymers with multiple non-centrosymmetric phases have sparked substantial research efforts in the materials community. We report the synthesis and properties of a hitherto unknown cadmium dicyanamide coordination polymer comprising benzyltrimethylammonium cations (BeTriMe+). The room-temperature (RT) crystal structure of [BeTriMe][Cd(N(CN)2)3] (BeTriMeCd) is composed of Cd centers linked together by triple dca-bridges to form one-dimensional chains with BeTriMe+ cations located in void spaces between the chains. The structure is polar, the space group is Cmc21, and the spontaneous polarization in the c-direction is induced by an arrangement of BeTriMe+ dipoles. BeTriMeCd undergoes a second-order phase transition (PT) at T1 = 268 K to a monoclinic polar phase P21. Much more drastic structural changes occur at the first-order PT observed in DSC at T2 = 391 K. Raman data prove that the PT at T2 leads to extensive rearrangement of the Cd-dca coordination sphere and pronounced disorder of both dca and BeTriMe+. On cooling, the HT polymorph transforms at T3 = 266 K to another phase of unknown symmetry. Temperature-resolved second harmonic generation (TR-SHG) studies at 800 nm confirm the structural non-centrosymmetry of all the phases detected. Optical studies indicate that BeTriMeCd exhibits at low temperatures an intense emission under 266 nm excitation. Strong temperature dependence of both one-photon excited luminescence and SHG response allowed for the demonstration of two disparate modes of optical thermometry for a single material. One is the classic ratiometric luminescence thermometry employing linear excitation in the ultraviolet region while the other is single-band SHG thermometry, a thus far unprecedented subtype of nonlinear optical thermometry. Thus, BeTriMeCd is a rare example of a dicyanamide framework exhibiting polar order, SHG activity, photoluminescence properties and linear and nonlinear optical temperature sensing capability.

One- and two-photon solvatochromism of the fluorescent dye Nile Red and its CF3, F and Br-substituted analogues.

The solvatochromic fluorophore Nile Red, 9-diethylamino-5H-benzo[a]phenoxazine-5-one, is one of the most commonly used stains to enhance contrast of lipid-rich areas of microscopic biosamples. Quite surprisingly, relatively little is known about the spectrally-resolved two-photon absorption (2PA) properties of this dye despite its promising features for two-photon microscopy of biological matter. For this reason, the two-photon solvatochromism of Nile Red still remains an uncharted territory as well. Also, no study has yet reported on how electron-withdrawing substituents attached to the Nile Red backbone affect its solvatochromic properties and two-photon brightness. In this paper, we demonstrate how solvent polarity influences the one- and two-photon absorption spectra of Nile Red as well as its fluorescence parameters, and we present new analogues that contain -CF3, -F and -Br substituents on its eastern side. Two-photon excited fluorescence experiments in a broad spectral range (780-1240 nm) and electronic structure calculations show that both the nature and location of the substituent have particular influence on the strength of 2PA, peaking in all cases at approx. 860 and 1050 nm. 2PA cross sections are higher at 1050 nm than at 860 nm, which suggests that Nile Red and its analogues are best suited for two-photon imaging employing excitation in the NIR-II optical transparency window of biological tissues.