Synthesis and Characterization of a Series of Monometallo-, Bimetallo-, and Heterobimetallo-1,2-Ethene-Linked Cofacial Bisporphyrins

The stepwise synthesis and characterization of a family of
selectively metalated
1,2-bis[5-(2,3,7,8,12,13,17,18-octaethylporphyrinyl)]ethenes is described. These compounds
are distinct from most of the previously reported
bisporphyrin systems which possessed rigid linking groups or multiple
strapping units, and their syntheses offer
several advantages over the previously prepared systems. Among the
members of this family we report the first
heterobimetallic bisporphyrins able to exist as either cis (cofacial)
or trans (extended) isomers including cis 13
{[NiII][ZnII]}, cis 14
{[NiII][CuII]}, and
trans 15
{[CuII][MnIII]}.
Products were characterized by 1H NMR
spectroscopy (except those containing CuII and/or
MnIII), visible spectroscopy, mass spectrometry, and
elemental
analyses. X-ray structural data are provided for bisporphyrins
4, 10, and 13−15:  cis
4
(C74H88N8Co2),
monoclinic,
space group P21/c, a =
21.097(15) Å, b = 14.120(5) Å, c
= 22.987(11) Å, β = 108.59(4)°, Z = 4;
cis 10
(C74H90N8Cu) monoclinic, space
group P21/n, a =
19.695(5) Å, b = 14.427(3) Å, c =
24.679(6) Å, β = 112.72(2)°, Z = 4; cis 13
(C74H88N8NiZn) monoclinic,
space group P21/c, a =
21.187(3) Å, b = 13.9091(11) Å, c
=
22.682(3) Å, β = 108.674(10)°, Z = 4; cis
14 (C74H88N8NiCu)
monoclinic, space group P21/c,
a = 21.169(3) Å,
b = 13.875(2) Å, c = 22.660(3) Å,
β = 108.64(9)°, Z = 4; trans 15
(C74H88N8CuMnCl), triclinic,
space group
P1̄, a = 9.8123(13), b =
13.742(3), c = 14.774(3), α = 83.26(2),
β = 78.532(12), γ = 78.347(14), Z =
1.

本研究报道了一系列选择性金属化1,2-双[5-(2,3,7,8,12,13,17,18-八乙基卟啉基)]乙烯的分步合成与表征。
该系列化合物与此前多数已报道的带有刚性连接基团或多套缚合单元的双卟啉（bisporphyrin）体系存在显著差异，且其合成路线相较已报道的同类体系具备多项优势。
在该系列化合物中，我们首次报道了可分别以顺式（共面）或反式（伸展）异构体形式存在的异双金属双卟啉，包括顺式13{[Ni(II)][Zn(II)]}、顺式14{[Ni(II)][Cu(II)]}以及反式15{[Cu(II)][Mn(III)]}。
所有产物均通过1H核磁共振波谱法（含Cu(II)和/或Mn(III)的样品除外）、可见光谱法、质谱法以及元素分析完成表征。
本研究还提供了双卟啉4、10及13~15的X射线结构数据：顺式4（C74H88N8Co2），单斜晶系，空间群P21/c，晶胞参数a=21.097(15) Å，b=14.120(5) Å，c=22.987(11) Å，β=108.59(4)°，Z=4；顺式10（C74H90N8Cu），单斜晶系，空间群P21/n，晶胞参数a=19.695(5) Å，b=14.427(3) Å，c=24.679(6) Å，β=112.72(2)°，Z=4；顺式13（C74H88N8NiZn），单斜晶系，空间群P21/c，晶胞参数a=21.187(3) Å，b=13.9091(11) Å，c=22.682(3) Å，β=108.674(10)°，Z=4；顺式14（C74H88N8NiCu），单斜晶系，空间群P21/c，晶胞参数a=21.169(3) Å，b=13.875(2) Å，c=22.660(3) Å，β=108.64(9)°，Z=4；反式15（C74H88N8CuMnCl），三斜晶系，空间群P-1，晶胞参数a=9.8123(13) Å，b=13.742(3) Å，c=14.774(3) Å，α=83.26(2)°，β=78.532(12)°，γ=78.347(14)°，Z=1。