Acenaphtho[1,2‐d][1,2,3]triazole and Its Kuratowski Complex: A π‐Extended Tecton for Supramolecular and Coordinative Self‐Assembly

Abstract

π‐Extended acenaphtho[1,2‐d][1,2,3]triazoles, the unsubstituted Anta‐H and its di‐tert‐butyl derivative Dibanta‐H, as well as 5,6,7,8‐tetrahydro‐1H‐naphtho[2,3‐d][1,2,3]triazole Cybta‐H were obtained in concise syntheses. In the solid state, Dibanta‐H forms an unprecedented hydrogen‐bonded cyclic tetrad, stabilized by dispersion interactions of the bulky tBu substituents, whereas a cyclic triad was found in the crystal structure of Anta‐H. These cyclic assemblies form infinite slipped stacks in the crystals. Evidence for analogous hydrogen‐bonded self‐assembly in solution was provided by low‐temperature NMR spectroscopy and computational analyses. Kuratowski‐type pentanuclear complexes [Zn5Cl4(Dibanta)6] and [Zn5Cl4(Cybta)6] were prepared from the respective triazoles. In the Dibanta complexes, the π‐aromatic surfaces of the ligands extend from the edges of the tetrahedral Zn5 core, yielding an enlarged structure with significant internal molecular free volume and red‐shifted fluorescence.

Heteropentanuclear {Ru(II)Cu(II)4} Kuratowski Complexes Assembled from a Ruthenium(II) Precursor Complex to Study Competing Exchange Interactions in M(II)(ta)2 Networks [ta(−) = 1,2,3-Triazolate]

“…1,2,3-Triazoles are nitrogen-containing heterocycles, known for forming a wide variety of coordination structures, e.g., homo- − or heteronuclear complexes, , coordination polymers, − and metal–organic frameworks (MOFs). − A feature of these structures can be metal-centered {MM 4 } tetrahedra which have recently been subject of detailed magnetic studies. − The pentanuclear Kuratowski complexes are coordination structures with this characteristic, which have been intensely investigated in our group. − These complexes consist of one central metal ion coordinated octahedrally by six 1,2,3-triazolates and four peripheral metal ions which span a tetrahedron around the center . Within this structure, the central metal ion is bound to the middle (N 2 ) of the three N-donor atoms of the triazole ring system.…”

Synthesis, Thermal Stability and Magnetic Properties of an Interpenetrated Mn(II) Triazolate Coordination Framework

“…Other bistria-zolate-based frameworks were investigated for catalysis, [7] gas binding, [8][9][10] chirality, [11] magnetic behaviour, [12] or even electrical and proton conductivity. [13,14] Single triazolate ligands tend to form Kuratowski complexes, [15] which were recently proven to give interesting chromophores [16] or building blocks for the assembly of metal hydrogen-bonded organic frameworks [17] via functionalization of the ligand backbones. However, the 1H-1,2,3-triazole (H-ta) tends to form MOFs of the M II (ta) 2 -type, [18][19][20] which can be considered as a framework of condensed Kuratowski units.…”