The Self-Assembly of an Unexpected, Unique Supramolecular Triangle Composed of Rigid Subunits

Abstract

Ein supramolekulares Dreieck anstelle des erwarteten Quadrats resultiert aus der Reaktion eines kompakten, ditopen 90°‐Platin(II)‐Zentrums und des starrsten linearen aromatischen Linkers Pyrazin (siehe Bild). Die Charakterisierung dieser unerwarteten Spezies erfolgte in Lösung und in fester Phase.

Mononuclear gold(iii) complexes with diazanaphthalenes: the influence of the position of nitrogen atoms in the aromatic rings on the complex crystalline properties

“…The complexes 1-5 differ in the orientation of the azaaromatic ring plane with respect to the plane dened by the four donor atoms surrounding the Au(III) ion. In the crystals of 5, the two planes are perpendicular (89.98 (10) and 89.30 (9) for two independent molecules), they are somewhat inclined in the crystals of 3 (68.84(7) ), and achieve the values of 62.76(7) and 59.46 (9) in the crystals of 2 and 4, respectively, while in the crystals of 1, this interplanar angle is only 39.47 (5) .…”

“…As a result, in each of the investigated crystals (1-5), the square planar coordination around Au(III) is extended to square pyramidal or tetragonal bipyramidal due to the Au/Cl intermolecular interactions and the molecular packing is dominated by the intermolecular C-H/Cl hydrogen bonds, which outnumber the other types of the specic intermolecular interactions. Notably, the p/p stacking interactions play a signicant structural role only in the centrosymmetric crystals of [AuCl 3 (benzodiazine)] complexes (1 and 2) and become either much weaker or completely absent in a series of [AuCl 3 (naphthyridine)] crystals (3)(4)(5). Geometrical parameters describing the p/p stacking interactions are listed in Table S5.…”

“…For example, 1,6-naphthyridine derivatives were reported as a new class of compounds for nonlinear optics. 3 Due to their structural properties, N-heterocycles provide rigid building blocks for molecular architectures with various transition metals, [4][5][6] so they have been extensively utilized for the formation of numerous mononuclear and polynuclear metal complexes, [7][8][9][10][11][12] metallosupramolecular assemblies with desirable structures and properties, 13 as well as for the construction of structural and functional models of metalloenzyme active sites. [14][15][16] Another important reason for investigation of gold(III) chemistry with N-heterocycles stems from the nding that use of these ligands in the synthesis of gold(III) complexes enhances the stability of Au(III) ion under physiological conditions, allowing evaluation of gold(III) complexes as potential antitumor 17 and antimicrobial agents.…”

Coordination Assembly of the Water‐Soluble Ti4(embonate)6 Cages with Mn2+ Ions

“…Up to now, the search for novel MOCs has driven the exploration of different geometries . Among which, the tetrahedra (M 4 L 4 and M 4 L 6 ) as the simplest polyhedral have been increasingly developed, and many tetrahedral cages constructed from different metals centers have been synthesized, including Pd, Pt, Fe, Zn, Co and lanthanides . However, polynuclear‐titanium cages (PTCs) are still rarely reported.…”

Sterically‐Directed Consecutive and Size‐Selective Self‐Assembly of Palladium Diphosphane Complexes with an Ar‐BIAN Ligand: Unexpected Formation of Pentameric and Hexameric Aggregates

“…Consequently, a preferential formation of the tetrameric assembly could be achieved by increasing the size of the phenoxy group 10. However, predicting nuclearity is not always possible, as demonstrated by the unforeseen generation of trimeric species [Rh 2 (darf) 2 (ox)] 3 ,11 [Pt(PMe 3 ) 2 (pyr)] 3 6+ , 12a and [Ru(dmso) 2 (pyr)Cl 2 ] 3 12b (darf= N , N ′‐diarylformamidinate, dmso=dimethyl sulfoxide, ox=oxalate, pyr=pyrazine) in which the rigid bridging units (i.e., ox and pyr) were expected to construct tetrameric assemblies. Deviations from the sterically predicted behavior were also reported in studies with [M(P^P)] 2+ complexes (M=Pd, Pt; P^P=dppp, dppf, and depe; dppf=bis(diphenylphosphanyl)ferrocene; depe=bis(diethylphosphanyl)ethane) 13.…”