Nature of cyanoargentate bridges defining spin crossover in new 2D Hofmann clathrate analogues.

Chemical composition is leading among the numerous factors that determine the spin transition properties of coordination compounds. Classic dicyanometallic bridges {M(CN)2}- are commonly used to build Hofmann-like spin-crossover frameworks, but some extended bridges are also synthetically available. In this paper, we describe a successful synthesis of two very similar spin-crossover frameworks that differ in the cyanometallic bridges involved, namely [Fe(etpz)2{Ag(CN)2}2] (1) and {Fe(etpz)2[Ag2(CN)3][Ag(CN)2]} (2) (where etpz = 2-ethylpyrazine). Magnetic and Mössbauer studies demonstrated the occurrence of abrupt one-step high-spin (HS) ↔ low-spin (LS) transitions for both complexes. The spin transition temperatures are T1/2 ↓ = 233 K and T1/2 ↑ = 243 K for 1 and T1/2 ↓ = 188 K and T1/2 ↑ = 191 K for 2 with thermal hysteresis loops of 10 K for 1 and 3 K for 2. The bridging mononuclear [Ag(CN)2]- units and FeII cations assemble to form infinite 2D layers in the structure of 1. Interestingly, compound 2 forms 2D layers of FeII cations bridged by both binuclear [Ag2(CN)3]- and mononuclear [Ag(CN)2]- units. The structures of 1 and 2 comprise different types of intermolecular interactions including Ag⋯Ag and Ag⋯Netpz, which induce the creation of supramolecular 3D frameworks. The synergy between metallophilic interactions and the spin transition is also confirmed by the variation of Ag⋯Ag distances during spin crossover. The characterization of such analogues allowed us to analyze in detail the effect of the cyanometallic bridge on the structure of new frameworks and on the bistability in Hofmann-like complexes.

Carbon dioxide capture from air leading to bis-[N-(5-methyl-1H-pyrazol-3-yl-κN2)carbamato-κO]copper(II) tetra-hydrate.

A mononuclear square-planar CuII complex of (5-methyl-1H-pyrazol-3-yl)carbamate, [Cu(C5H6N3O2)2]·4H2O, was synthesized using a one-pot reaction from 5-methyl-3-pyrazolamine and copper(II) acetate in water under ambient conditions. The adsorption of carbon dioxide from air was facilitated by the addition of di-ethano-lamine to the reaction mixture. While di-ethano-lamine is not a component of the final product, it plays a pivotal role in the reaction by creating an alkaline environment, thereby enabling the adsorption of atmos-pheric carbon dioxide. The central copper(II) atom is in an (N2O2) square-planar coordination environment formed by two N atoms and two O atoms of two equivalent (5-methyl-1H-pyrazol-3-yl)carbamate ligands. Additionally, there are co-crystallized water mol-ecules within the crystal structure of this compound. These co-crystallized water mol-ecules are linked to the CuII mononuclear complex by O-H⋯O hydrogen bonds. According to Hirshfeld surface analysis, the most frequently observed weak inter-molecular inter-actions are H⋯O/O⋯H (33.6%), H⋯C/C⋯H (11.3%) and H⋯N/N⋯H (9.0%) contacts.

Crystal structure of bis-(3-carb-oxy-1-methyl-pyrid-inium) octa-bromide.

The crystal structure of the title salt, bis-(3-carb-oxy-1-methyl-pyridinium) octa-bromide, 2C7H8NO2 +·Br8 2-, consists of 3-carb-oxy-1-methyl-pyridinium (N-methyl-nicotinic acid) cations, which are stacked between relatively rare [Br8]2- anions. The polybromide [Br8]2- anion has point group symmetry and can be described as being composed of two [Br3]- anions connected with a Br2 mol-ecule in a Z-shaped manner. Contacts between neighboring octa-bromide anions ensure the creation of pseudo-polymeric chains propagating along [111]. The organic cations are located between anionic chains and are connected to each other through O-H⋯O hydrogen bonds and to the [Br8]2- anions through π⋯Br inter-actions that induce the creation of a supra-molecular tri-periodic network. In addition, the presence of weak C-H⋯Br contacts leads to the creation of layers, which align parallel to (11).

Structural diversity in proline-based lead bromide chiral perovskites.

Lead halide hybrid perovskites incorporating chiral organic cations attract considerable attention due to their promising application in multifarious optoelectronic devices. However, the examples of chiral hybrid perovskites are still limited, which greatly impedes their further studies in various optoelectronic fields. Herein, we report on new low-dimensional lead-halide hybrid perovskites incorporating the enantiopure chiral α-amino acid L-proline. Two hybrid perovskites (L-proH)PbBr3·H2O (Pro-PbBr3) and (L-proH)4Pb3Br10·4H2O (Pro-Pb3Br10) have been synthesized by employing different ratios of organic and inorganic precursors. According to structural analysis, the inorganic sublattice of compound Pro-PbBr3 is built of one-dimensional (1D) [PbX3]∞n- lead halide chains, whereas the inorganic sublattice of compound Pro-Pb3Br10 is built upon a rare two-dimensional (2D) [Pb3Br10]∞4n- honeycomb-type inorganic framework. Hirshfeld surface analysis revealed an important role of various hydrogen bonding interactions in providing the binding between organic and inorganic parts of these hybrid perovskites. The optical band gap values of new hybrid perovskites as estimated using the Tauc plot approach are 4.19 eV (Pro-PbBr3) and 4.13 eV (Pro-Pb3Br10). Also, new compounds display low-temperature broadband photoluminescence which can be attributed to the self-trapped excitons. These results show the potential of α-proline for constructing novel and highly demanded chiral hybrid perovskites, which will hold great promise for further optoelectronic applications.

Chiral 2D organic-inorganic hybrid perovskites based on L-histidine.

Novel chiral hybrid perovskites are highly demanded for various advanced applications such as spintronics, optoelectronics, photovoltaics etc. However, the scope of these new materials is still limited. Herein, we present new 2D hybrid perovskites based upon chiral α-amino acid L-histidine. The generalized formula of these new compounds can be denoted as (L-HisH)2PbBrxI4-x (where L-His = L-histidine; x = 4, 3, 2, 1, 0.4 and 0). All perovskites are characterized by a very similar structural motif that consists of corner-sharing lead halide octahedra arranged in one-layer thin inorganic slabs interleaved by organic layers established by L-histidinium(1+) cations. L-Histidine provides a breaking of spatial parity of these perovskites that results in their non-centrosymmetric crystal structures. These compounds show a multiband absorption up to 590 nm for iodide perovskite. In addition, new compounds display pronounced single-peak photoluminescence, which finely blue shifts upon the gradual substitution of iodine by bromine. New perovskites exhibit excellent thermal stability up to 490 K and 445 K for bromide and iodide compounds, respectively. These results show the ability of L-histidine to produce novel and highly demanded chiral hybrid perovskites.

Four-Step Spin Crossover in a New Cyano-Bridged Iron-Silver Coordination Polymer.

Spin-crossover complexes with multistep transitions attract much attention due to their potential applications as multi-switches and for data storage. A four-step spin crossover is observed in the new iron(II)-based cyanometallic guest-free framework compound Fe(2-ethoxypyrazine)2 {Ag(CN)2 }2 during the transition from the low-spin to the high-spin state. A reverse process occurs in three steps. Crystallographic studies reveal an associated stepwise evolution of the crystal structures. Multiple transitions in the reported complex originate from distinct FeII sites which exist due to the packing of the ligand with a bulky substituent.

Crystal structure of 9-amino-acridinium chloride N,N-di-methyl-formamide monosolvate.

9-Amino-acridinium chloride N,N-di-methyl-formamide monosolvate, C13H11N2 +Cl-·C3H7NO, crystallizes in the monoclinic space group P21/c. The salt was crystallized from N,N-di-methyl-formamide. The asymmetric unit consists of two C13H11N2 +Cl- formula units. The 9-amino-acridinium (9-AA) mol-ecules are protonated with the proton on the N atom of the central ring. This N atom is connected to an N,N-di-methyl-formamide mol-ecule by a hydrogen bond. The H atoms of the amino groups create short contacts with two chloride ions. The 9-AA cations in adjacent layers are oriented in an anti-parallel manner. The mol-ecules are linked via a network of multidirectional π-π inter-actions between the 9-AA rings, and the whole lattice is additionally stabilized by electrostatic inter-actions between ions.

Crystal structure of catena-poly[[[(2-eth-oxy-pyrazine-κN)copper(I)]-di-µ2-cyanido] [copper(I)-µ2-cyanido]].

In the asymmetric unit of the title coordination compound, {[Cu(CN)(C4H3OC2H5N2)][Cu(CN)]} n , there are two Cu atoms with different coordination environments. One CuI ion is coordinated in a triangular coordination geometry by the N atom of the 2-eth-oxy-pyrazine mol-ecule and by two bridging cyanide ligands, equally disordered over two sites exchanging C and N atoms, thus forming polymeric chains parallel to the c axis. The other Cu atom is connected to two bridging cyanide groups disordered over two sites with an occupancy of 0.5 for each C and N atom, and forming an almost linear polymeric chain parallel to the b axis. In the crystal, the two types of chain, which are orthogonal to each other, are connected by cuprophilic Cu⋯Cu inter-actions [2.7958 (13) Å], forming two-dimensional metal-organic coordination layers parallel to the bc plane. The coordination framework is further stabilized by weak long-range (electrostatic type) C-H⋯π inter-actions between cyano groups and 2-eth-oxy-pyrazine rings.