A convergent synthetic approach using sterically demanding aryldipyrrylmethanes for tuning the pocket sizes of cofacial bisporphyrins.
Meso substitution opposite to the spacer provides a convenient approach for tuning the pocket sizes of pillared cofacial bisporphyrins. The synthesis and coordination chemistry of xanthene and dibenzofuran anchored platforms structurally modified with 2,6-dimethoxyaryl groups are described. Comparative structural analysis of xanthene derivatives confirms the ability of the trans-aryl groups to adjust the vertical dimension of the cofacial cleft: 7 (C(97)H(106)Cl(4)N(8)O(5)), monoclinic, space group P2(1)/c, a = 28.8353(12) A, b = 17.1139(7) A, c = 17.5978(7) A, beta = 98.826(1) degrees, Z = 4; 8 (C(101)H(123)Cl(2)N(8)O(11.5)Zn(2)), monoclinic, space group P2(1)/n, a = 14.5517(6) A, b = 22.9226(10) A, c = 28.5155(13) A, beta = 90.312(14) degrees, Z = 4; 12 (C(99)H(102)Cl(14)N(8)O(5)Mn(2)), monoclinic, space group P2/c, a = 19.5891(3) A, b = 15.0741(2) A, c = 33.2019(6) A, beta = 91.947(10) degrees, Z = 4. The convenience and versatility of this synthetic method offers intriguing opportunities to specifically tailor the binding pockets of cofacial bisporphyrins for the study of small-molecule activation within a proton-coupled electron transfer framework.
Chang
Christopher J
CJ
Departments of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
Deng
Yongqi
Y
Peng
Shie-Ming
SM
Lee
Gene-Hsiang
GH
Yeh
Chen-Yu
CY
Nocera
Daniel G
DG
D001572:Benzofurans / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008345:Manganese / Q000737:chemistry*; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D008697:Methane / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism; D014966:Xanthenes / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*
D001572:Benzofurans; D008665:Metalloporphyrins; D014966:Xanthenes; D008345:Manganese; D007501:Iron; D015032:Zinc; C105430:benzofuran; D008697:Methane