s‐Tetrazine as Ligand for Monomeric and Bridged Macrocyclic Metal Complexes

Abstract

Good semiconductor properties are exhibited by stable bridged metal complexes containing s‐tetrazine as an N‐donor ligand. Square‐planar metal complexes, for example, phthalocyaninatoruthenium(II) and 2,3‐naphthalocyaninatoiron(II), may be bridged. The structure of this hexcoordinated bridged polymer is indicated in formula 1.

Novel s-tetrazine-based dyes with enhanced two-photon absorption cross-section

“…The low LUMO energy of tetrazine derivatives enables inverse demand Diels-Alder cycloaddition reactions as a heterodiene [1][2][3][4][5][6][7][8][9][10][11][12][13] and stabilizes the anionic intermediate that enables aromatic nucleophilic substitution. [14][15][16][17][18][19] Tetrazine derivatives are also used in coordination chemistry [20][21][22][23][24] because they can form complexes with electron-rich metals. In addition, some tetrazine derivatives show strong electrofluorochromism [25][26][27][28][29][30][31][32] and have been utilized in pollutant detection.…”

Metallomacrocycle (MacM) complex with cyanide as bridged ligand: Electronic structures of [MacMCN]n

“…The electrical properties exhibited by these systems have attracted much attention 27, 28. For instance, the bridged transition metal compounds are fairly stable polymers that exhibit intrinsic conductivities, without external oxidative doping.…”

Structural Investigations of Oligomeric Axially Bridged Ruthenium Phthalocyanines by EXAFS Spectroscopy

“…[13] (PcRu) 2 reacts easily with ligands L such as pyrazine, stetrazine, 1,4-diisocyanobenzene and others to form the corresponding monomers PcRu(L) 2 , and under somewhat different conditions to form the bridged systems [PcRu(L)] n . [4,14] Although the monomeric complexes PcM(L) 2 (L ϭ pyz, tz, dib; M ϭ Fe, Ru, Os) are all insulators, it can be seen that the ligand (L) has a significant effect on the conductivity of the bridged complexes [PcM(L)] n : as 1,4-diazabicyclo[2.2.2]octane (dabco) is a ligand containing no π-orbitals to interact with the metallomacrocycle the [PcM(dabco)] n complexes are also insulators, [2] whereas an increase in electrical conductivity is observed for the pyrazine-and 1,4-diisocyanobenzene-bridged compounds. [PcRu(pyz)] n (2) and [PcRu(dib)] n (3) exhibit electrical conductivities (σ RT ϭ 1 ϫ 10 Ϫ7 S cm Ϫ1 and σ RT ϭ 2 ϫ 10 Ϫ6 S cm Ϫ1 ) [4,15] in the low semiconducting region.…”