A phthalocyanine–subphthalocyanine heterodinuclear dimer: comparison of spectroscopic properties with those of homodinuclear dimers of constituting units

Abstract

A phthalocyanine-subphthalocyanine heterodinuclear dimer has been disclosed for the first time with its unique flat-bowl-shaped structure revealed by X-ray crystallography. Its spectroscopic properties were compared with those of homodinuclear dimers of constituting units, as well as those of constituting monomeric units.

Cyclophanes Containing Bowl‐Shaped Aromatic Chromophores: Three Isomers of anti‐[2.2](1,4)Subphthalocyaninophane

“…TheT DDFT calculations estimated that the Qbands mainly consist of transitions between the six frontier molecular orbitals (MOs), the HOMO-1 and HOMO,a nd the LUMO-LUMO + 3, which are ascribed to products of linear combinations of the HOMO and the LUMO and LUMO + 1o fM1 (Figure 4; see also Table S1 in the Supporting Information). In the case of the homo-and heterodimer systems of Pc, SubPc, and related analogues sharing p-conjugated aromatic rings,s uch as benzene,n aphthalene,a nd anthracene, [19][20][21][22][23][24] the frontier MOs are known to be similarly developed by linear combination of the frontier MOs of the corresponding monomer species.I nt his respect, the through-space expansion of the conjugated systems through the cyclophane bridge in the case of the current SubPc dimer species was supported in theory. In fact, acertain amount of the MO coefficient was observed between the benzene rings of the cyclophane unit for the LUMO + 1o fCC and the LUMO of CV and VV (see Figures S3-S5).…”

Trifluoroethoxy‐Coated Subphthalocyanines Attract Small Arenes in Their π‐Concave Cavity

“…[3, 5a] The fully trifluoroethoxy-coated Pc-SubPc heterodinuclear dimer 2 has au nique combination of af lat Pc structure and ab owl-shaped SubPc structure, as wasr evealed by X-ray crystallography in 2014( Figure 1b). [6] Interestingly, we found that toluene was attracted to the concave p-surface of the SubPc moiety of 2.F ollowing the X-ray crystallographic analysiso f2,w eh ave been interested in the potentialo f SubPc/arene clathrates. The concave p-surface space in SubPcs should be useful for trapping small arene compounds and the resultingc lathrates should be suitable for X-ray crystallographic analysis.…”

“…We found that dispersion interactions are the major impetusf or clathrate formation while the contributions of fluorinee ffects and electrostatic interactions to the attraction are not large. Since trifluoroethoxy-coated SubPcs are stable and easy to synthesize andh andle, [3,5,6] they may serve as at ool for the crystallization of small, noncrystalline aromatic compounds in the form of trifluoroethoxy-coated SubPc/arene clathrates (Figure 1c).…”

“…We also determined the X-ray crystal structures of SubPc dimers 3,i ncluding the fully trifluoroethoxy-coated SubPc homo-dimer 3a and the partially trifluoroethoxy-coated SubPc hetero-dimer 3b. [6] In these dimers, the two SubPc units are connected by a p-hydroquinone linker (Figure 3a). Crystalliza-tion of the dimers 3 was attempted from either toluene or benzene.…”

Cyclophanes Containing Bowl‐Shaped Aromatic Chromophores: Three Isomers of anti‐[2.2](1,4)Subphthalocyaninophane

“…The TDDFT calculations estimated that the Q bands mainly consist of transitions between the six frontier molecular orbitals (MOs), the HOMO-1 and HOMO, and the LUMO-LUMO + 3, which are ascribed to products of linear combinations of the HOMO and the LUMO and LUMO + 1 of M1 (Figure 4; see also Table S1 in the Supporting Information). In the case of the homo-and heterodimer systems of Pc, SubPc, and related analogues sharing p-conjugated aromatic rings, such as benzene, naphthalene, and anthracene, [19][20][21][22][23][24] the frontier MOs are known to be similarly developed by linear combination of the frontier MOs of the corresponding monomer species. In this respect, the through-space expansion of the conjugated systems through the cyclophane bridge in the case of the current SubPc dimer species was supported in theory.…”