Synthesis and Electronic Properties of Tetrakis[4-(pyrimidyl)phenyl]methanes − A Novel Class of Electronically Active Nanometer-Sized Scaffolds

Abstract

Tetrakis [4-(arylpyrimidyl)phenyl]methanes 4 can be readily synthesized by using a highly convergent vinamidinium salt cyclocondensation strategy. The conjugated side-chains of

Electrolysis of Tetrakis(4-N,N-dimethylammophenyl)methane -Fragmentation of a Tetraarylmethane under Oxidative Conditions

“…Recently, we could show that electron deficient tetrakis(pyrim idylarylene) m ethanes (1: R E D O X = 5-R-pyrimidin-2-yl) display a cooperative reduction behavior between the individual branches of the tetrahedra [7]. According to cyclic voltam m etry quasi reversible redox cycles indicate an electrochemically m ediated bispirocyclization that can be perform ed repeatedly in several cycles.…”

The First Synthesis and Electronic Properties of Tetrakis[(hetero)phenanthrenyl]methanes

“…The sp 3 ‐hybridized center links four substituents with extended π‐systems in the sense of homoconjugation, simultaneous mutual orthogonality, and high degeneracy of the molecular orbitals of the conjugated chains 5. Although quite a number of functionalized tetrakis(arylene)methane tetrahedra with organometallic,6 porphyrin,4d,7 pyrimidyl,8 and oxadiazole9 substitution at their peripheries have been prepared in recent years, the class of condensed and annealed (hetero)aromatic systems directly linked to the sp 3 ‐hybridized center has so far remained unknown. In particular, four phenanthrenyl or naphthoheteroaryl substituents brought together in close proximity might display interesting emission and/or electrochemical behavior.…”

“…In particular, four phenanthrenyl or naphthoheteroaryl substituents brought together in close proximity might display interesting emission and/or electrochemical behavior. As part of our program directed towards exploration of the synthesis and electronic properties of novel tetraarylmethanes with electro‐ and fluorophores,8,10 we have also focussed on sterically loaded systems. Here we wish to report the first synthesis of tetrakis[(hetero)phenanthryl]methanes and the first investigations of their electronic properties (absorption and emission spectra, cyclic voltammetry).…”

Convenient Syntheses of Tetraarylmethane Starting Materials

“…substituents in close proximity and in the sense of a homoconjugation, resulting in simultaneous mutual orthogonality and a high degeneracy of the molecular orbitals of the conjugated chains. 5 In the past years quite a number of functionalized tetrakis(arylene)methane tetrahedra with organometallic, 6 porphyrine, 4d,7 pyrimidyl, 8 oxadiazole, 9 and phenanthrenyl 10 substitution have been prepared. As part of our program directed towards the syntheses and electronic properties of novel tetraarylmethanes with electro-and fluorophores 8,10,11 we also have focussed on the access to suitable starting materials.…”

“…5 In the past years quite a number of functionalized tetrakis(arylene)methane tetrahedra with organometallic, 6 porphyrine, 4d,7 pyrimidyl, 8 oxadiazole, 9 and phenanthrenyl 10 substitution have been prepared. As part of our program directed towards the syntheses and electronic properties of novel tetraarylmethanes with electro-and fluorophores 8,10,11 we also have focussed on the access to suitable starting materials. Here, we wish to report an improved synthetic protocol for the large scale preparation of the mother compound of all tetraarylmethane syntheses, tetraphenylmethane (1), and convenient and high yielding syntheses of a couple of functionalized tetraarylmethanes.…”