METALLOMACROCYCLE COMPLEX BRIDGED POLYMERS: ELECTRONIC STRUCTURE OF -[MacM(L)]n

Abstract

The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocy ninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.The electronic structures of one-dimensional metallomacrocycles with bidentate bridging ligands, such as –[MacM(L)]n (Mac=phthalocyaninato dianion, tetrabenzoporphyrinato dianion; M=Fe(II), Ru(II), Os(II); L=dabco, pyrazine, triazine, tetrazine (tz), 4,4'-bipyridine, bipyridyacetylene, bis(4-pyridyl)ethylene, bis(4-pyridyl)bencene) have been studied using the tight-binding solid state extended Hückel. The results of this study have shown that the intrinsic semiconductivity properties depend on several factors: (i) the valence band is composed largely of the transition metal dxy orbital; and (ii) the conduction band is composed of a mixture between the macrocycle and bridged orbitals for systems formed by pyrazine, triazine, bipyridine, bipyridyacetylene, etc. However, this composition is different when the ligand tetrazine is used. Such a band is formed by the ? system of tetrazine ligand.