Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

Abstract

Herein, we report the use of sterically invariant carborane-based chalcogenols, containing exopolyhedral B-Se or B-S bonds, as ligands for the formation of photoluminescent copper(I)based metal-organic chalcogenolate assemblies (MOCHAs). We show that precise tuning of the carborane dipole by changing the carborane isomer from meta-to ortho-allows for control over the MOCHA morphology and regulation of the resulting photophysical properties. Furthermore, microcrystal electron diffraction (MicroED) has been demonstrated as a powerful tool for metal chalcogenide structure elucidation. Through the use of MicroED, one of the isolated materials is determined to consist of zero-dimensional Cu 4 (Se-C 2 B 10 H 11 ) 4 clusters with an unprecedented Cu 4 Se 4 geometry.

Carborane-thiol protected copper nanoclusters: stimuli-responsive materials with tunable phosphorescence

“…Literature reports on the magnitude of dipole moment and alteration in the orientation of carboranes upon binding with the metal surface indicate changes in their electronic properties upon binding with metal atoms. 62–64…”

“…Literature reports on the magnitude of dipole moment and alteration in the orientation of carboranes upon binding with the metal surface indicate changes in their electronic properties upon binding with metal atoms. [62][63][64] Infrared (IR) and Raman spectroscopy were performed to understand the vibrational spectral signatures of these clusters. The IR spectra of Cu 4 @oCBT, Cu 4 @mCBT and Cu 4 @ICBT are shown in Fig.…”

“…Color code: orange = copper, yellow = sulfur, pink = boron, violet = iodine, gray = carbon and green = hydrogen.The13 C NMR spectra showed a single peak at δ 54.51 ppm due to C 1 and C 7 carbons of M 9 ligand, which got split to δ 56.37 and 49.99 ppm for Cu 4 @mCBT and the peaks at δ 45.97 and 44.41 ppm of I 9 ligands were shifted to δ 51.50 and 46.91 ppm, respectively for Cu 4 @ICBT (Fig.S22 and S24). Literature reports on the magnitude of dipole moment and alteration in orientation of carboranes upon binding with the metal surface indicate changes in their electronic properties upon binding with metal atoms [62][63][64].…”

Macropolyhedral syn-B18H22, the “Forgotten” Isomer

“…Boron hydrides as functional molecules, going beyond alkanethiols in their structural diversity for self-assembled monolayers (SAMs), are potentially very interesting and stable 2D materials for filtration technology due to their symmetry, limited conformational flexibility, well-defined, and different to-carbon-chemistries and other unique aspects such as thickness, and porosity adjusted in the subnanometer range or extraordinary thermal and chemical stability. − These engineered cage molecules may interact in different ways to provide control over surface interactions. , The advantage of boron hydrides as building blocks of SAMs over many linear chain systems is that simple cage molecules do not exhibit domain boundaries caused by the orientation of molecular tilt, with respect to the surface normal. ,, The first boron cage, Cs 2 [B 12 H 11 SH], was employed to study SAMs on gold surfaces in 1998 . Mercapto-functionalized cage molecules provided great control over surface responses, a higher order of supramolecular assembly, and eventually a precise three-dimensional assembly over a surface. ,, However, the SAMs of boron hydrides still remain much less explored than those of alkanethiol derivatives, and macropolyhedral borane derivatives assembled on metal or other substrate surfaces have not been investigated yet.…”

XFEL Microcrystallography of Self-Assembling Silver n-Alkanethiolates

“…Metal–organic chalcogenolates (MOChas) are self-assembling coordination polymers of a metal and an organic source of sulfur, selenium, or tellurium. Recently, compounds in this family have attracted interest for semiconducting properties, light–matter interactions, and catalytic activity. − Silver n- alkanethiolates − have drawn consistent interest as three-dimensional analogues to the well-studied self-assembled monolayers (SAMs) on silver and gold metal surfaces and for their antimicrobial activity . However, a lack of a single-crystal structure because of small crystal sizes is a common refrain in reports of these and related compounds.…”