A Novel Family of Polyiodo‐Bromoantimonate(III) Complexes: Cation‐Driven Self‐Assembly of Photoconductive Metal‐Polyhalide Frameworks

Abstract

In the presence of different cations, reactions of [SbBr ] and I result in a new family of diverse supramolecular 1D polyiodide-bromoantimonate networks. The coordination number of Sb, as well as geometry of assembling {I } polyhalide units, can vary, resulting in unprecedented structural types. The nature of I⋅⋅⋅Br interactions was studied by DFT calculations; estimated energy values are 1.6-6.9 kcal mol . Some of the compounds showed strong photoconductivity in thin films, suggesting multiple feasible applications in optoelectronics and solar energy conversion.

Symmetrical Noncovalent Interactions Br···Br Observed in Crystal Structure of Exotic Primary Peroxide

“…The quantum theory of atoms in molecules (QTAIM) analysis [27] and independent gradient model analysis of noncovalent interactions based The appropriate bond critical point for intermolecular noncovalent interactions Br···Br in the single-crystal XRD structure of 3 was found during the QTAIM analysis. The properties of electron density in this bond critical point are typical for noncovalent interactions [29,30] and, in particular, for similar weak contacts halogen···halogen [31][32][33]. Energy for these contacts (2.2-2.5 kcal/mol) was estimated using the procedures developed by Tsirelson et al for non-covalent contacts involving bromine atoms using the equations E int = 0.58(−V(r)) or E int = 0.57G(r), respectively [28].…”

Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine

“…[49] Working in the highlya cidic media results in forma-tion of ionic compounds of different types, featuring pyridinium cations and SbBr 6 3À and Sb 2 Br 9 3À anions. [50][51][52] Recently,t he structureso ft wo molecular SbCl 3 complexes with Py have been determined by our group. [53] In both structures Cl•••Sb pnictogen bonds, where Sb acts as Lewis acid, are evident on the basis of the quantumc hemical computations.…”

“…One of the reason for absence of the molecular complexes of antimony trihalides is their high affinity to water, which results in the formation of ionic hydrolysis products like [HPy] + 2 [Sb 2 OBr n Cl 6− n ] 2− ( n =0,2,4) [49] . Working in the highly acidic media results in formation of ionic compounds of different types, featuring pyridinium cations and SbBr 6 3− and Sb 2 Br 9 3− anions [50–52] …”

New Crystal Forms for Biologically Active Compounds. Part 1: Noncovalent Interactions in Adducts of Nevirapine with XB Donors

“…In order to confirm or disprove the hypothesis on the existence of these supramolecular contacts and quantify their energies from a theoretical standpoint, we carried out DFT calculations and performed topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method) [73] for the (NVP) 4 •(1,4-FIB) 3 and (NVP) 3 •(1,3-DIB) 3 model supramolecular cluster (Supporting Information, Table S3). We have already used a similar approach to study noncovalent interactions (e.g., hydrogen, halogen and chalcogen bonding, metallophilic interactions, stacking) in various organic, organometallic and coordination compounds [42][43][44][86][87][88][89]. The results of these calculations are summarized in Table 2 Table 2.…”