Abstract
Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H4A) and adjacent (cisoid, H4B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H8A4+/H8A4+ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H4A/H4B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1: I complex. The Zn2A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 Å. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 Å. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.
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Collman P, Wagenknecht P S and Hutchison J E 1994 Angew. Chem. Int. Ed. Engl. 33 1537
Nam W, Han H J, Oh S-Y, Lee Y J, Choi M-H, Han S-Y, Kim C, Woo S K and Shin W 2000 J. Am. Chem. Soc. 122 8677
Otsuka S and Yamanaka T (eds) 1988 Metalloproteins: Chemical properties and biological effects (Amsterdam: Elsevier)
Ravikanth M and Chandrashekar T K 1995 Structure and Bonding 82 105
Heiler D, McLendon G and Rogalskyj P 1987 J. Am. Chem. Soc. 109 604
Tabushi I and Kugimiya S 1986 J. Am. Chem. Soc. 108 6926
Sessler J L, Johnson M R, Lin T-Y and Creager S E 1988 J. Am. Chem. Soc. 110 3659
Jeyakumar D and Krishnan V 1992 Spectrochimica Acta A48 1671
Tian H-J, Zhou Q-F, Shen S-Y and Xu H-J 1993 J. Photochem. Photobiol. A: Chem. 163
Anderson H L, Hunter C A, Meah M N and Sanders J K M 1990 J. Am. Chem. Soc. 112 5780 and references therein
Danks I P, Lane T G, Sutherland I O and Yep M 1992 Tetrahedron 42 7699
Collman J P, Tyvoll D A, Chang L L and Fish H T 1995 J. Org. Chem. 60 1926
Chang K, Liu H Y and Abdalmuhdi I 1984 J. Am. Chem. Soc. 106 2725
Leighton, Cowan J A, Abraham and R J and Sanders J K M 1988 J. Org. Chem. 53 733
Collman P, Denisevich P, Konai Y, Marrocco M, Koval C and Anson F C 1980 J. Chem. Soc. Chem. Commun. 6027
Collman J P, Anson F C, Bencosme S, Chong A, Collins Y, Denisevich P, Evitt E, Geiger T, Ibers J A, Jameson G, Konai Y, Koval C, Meier K, Oakley P, Pettman R, Schmittou E and Sessler J 1981 Organic Synthesis: Today and tomorrow (eds) B M Trost and C R Hutchinson (Oxford: Pergaman Press) 29
Collman J P, Elliot C M, Halbert T R and Tovrog B S 1977 Proc. Natl. Acad Sci. USA 74 18
Kagan E, Mauzerall D and Merrifield R B 1977 J. Am. Chem. Soc. 99 5484
Kagan N E 1979 Porphyrin chemistry advances (ed.) F R Longo Ann. Arbor. Sci. 43
Karaman, Blasko A, Almarsson O, Arasasingam R and Bruice T C 1992 J. Am. Chem. Soc. 114 4889
Landrum, Reed C A, Hatano K and Scheidt W R 1978 J. Am. Chem. Soc. 100 3232
Neumann K H and Vogle F 1988 J. Chem. Soc. Chem. Commun. 520
Golubchikov O A, Korovina S G, Kuvshinova E M, Semeikin A S, Shul’ga A M, Perfil’ev V A, Syrbu S A and Berezin B D 1989 J. Org. Chem. USSR (Engl. Transl.) 2144
Hunter A, Meah M N and Sanders J K M 1990 J. Am. Chem. Soc. 12 5773
Anderson H L, Bashall A, Henrick K, McPartlin M and Sanders J K M 1994 Angew. Chem. 33 429
Uemori Y, Nakatsubo A, Imai H, Nakagawa S and Kyuno E 1992 Inorg. Chem. 31 5164
Imai H and Uemori Y 1994 J. Chem. Soc. Perkin Trans. 2 1793
Anderson H L and Sanders J K M 1995 J. Chem. Soc. Perkin Trans 1, 2223
Anderson H L, Anderson S and Sanders J K M 1995 ibid 2231
Anderson S, Anderson H L and Sanders J K M 1995 ibid 2247 and 2256
Mackay L G, Anderson H L and Sanders J K M 1995 ibid 2269
Wylie R S, Levy E G and Sanders J K M 1997 Chem. Commun. 1611
Chang, Kuo M-S and Wang C-B 1977 J. Heterocycl. Chem. 14 943
Chang C K 1977 J. Heterocycl. Chem. 14 1285
Collman J P, Bencosme C S, Barnes C E and Miller B D 1983 J. Am. Chem. Soc. 105 2704
Collman J P, Denisevich P, Konai Y, Marrocco M, Koval and Anson F C 1980 J. Am. Chem. Soc. 102 6027
Karaman R, Jeon S, AImarsson O and Bruice T C 1992 J. Am. Chem. Soc. 114 4899
Crossley, Harding M M and Sternhell S 1992 J. Org. Chem. 57 1833
Sun, Martell A E and Tsutsui M 1986 J. Heterocycl. Chem. 23 561
Walter I, Ojadi E C A and Linschitz H 1993 J. Phys. Chem. 97 13308
Ojadi E C A, Linschitz H, Gouterman M, Walter R I, Lindsey J S, Wagner R W, Droupadi P R and Wang W 1993 J. Phys. Chem. 97 13192
Hunter, Leighton P and Sanders J K M 1989 J. Chem. Soc. Perkin Trans. 1 547
Mest, L’Her M, Hendricks N H, Kim K and Collman J P 1992 Inorg. Chem. 31 835
Danks, Sutherland I O and Yap C H 1990 J. Chem. Soc. Perkin Trans. 1 421
Fleischer C K, Miller L E and Webb 1964 J. Am. Chem. Soc. 86 2342
Glick M D, Cohen G H and Hoard J L 1967 J. Am. Chem. Soc. 89 1996
Scheidt W R, Kastner M E and Hatano K 1978 Inorg. Chem. 17 706
Hatana K, Kawasaki K, Munakata S and Iitaka Y 1987 Bull. Chem. Soc. Jpn. 60 1985
Bym, Curtis C J, Goldberg I, Hsiou Y, Khan S I, Sawin P A, Tendick S K and Strouse C E 1991 J. Am. Chem. Soc. 113 6549
Hunter and Sanders J K M 1991 J. Am. Chem. Soc. 112 5525
Bhyrappa P and Krishnan V 1991 Inorg. Chem. 30 239
Hill 1910 Physiol. London 40 IV–VII
Sheldrick 1986 SHELXS-86 Program for crystal structure determination, University of Gottingen, Republic of Germany
Sheldrick 1976 SHELXS-76 Program for crystal structure determination, University of Cambridge, UK
Vaijayanthimala G 1996 Ph D thesis, see details for figures 12–13, Indian Institute of Science, Bangalore, India
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Vaijayanthimala, G., Krishnan, V. & Mandal, S.K. Cyclic porphyrin dimers as hosts for coordinating ligands. J Chem Sci 120, 115–129 (2008). https://doi.org/10.1007/s12039-008-0014-3
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DOI: https://doi.org/10.1007/s12039-008-0014-3