Skip to content

Research at St Andrews

Structural diversity in tetrakis(4-pyridyl)porphyrin supramolecular building blocks

Research output: Contribution to journalArticle


Open Access Status

  • Embargoed (until 19/04/20)


Manish Kumar Mishra, Hemant Choudhary, David B. Cordes, Steven Kelley, Robin Rogers

School/Research organisations


In memory of a pioneer in crystal engineering, Prof. Israel Goldberg, we report a series of new framework solids, based on the ligand tetrakis(4–pyridyl)porphyrin (TPyP). Spontaneous reactions of TPyP with seven different metal salts under liquid-liquid diffusion at ambient temperature show that the formation of ionic compounds is preferred to coordination polymers due to increased conformational freedom. Two coordination networks, {(HgI2)2(TPyP)}n·4nCHCl3∙2nTCE (TCE = 1,1,2,2–tetrachloroethane), and {(Ba(μ1,1–NCS)(μ1,1,3–NCS)(H2O)(MeCN))2(TPyP)}n·4nH2O, displayed a new isomeric form of the known [(HgI2)2(TPyP)] polymeric motif, and a two-dimensional honeycomb polymeric motif linked by hydrogen-bonding into a three dimensional moganite (mog) net, respectively. Four protonated porphyrinic salts, [H3TPyP][PF6]3∙0.5TCE, [H2TPyP][I3]2·2MeOH, [H4TPyP][UO2Cl4]2·6MeCN, and [H4TPyP][Th(NO3)6][NO3]2, were observed which hydrogen bond to give one- or two-dimensional networks, or in the case of [H4TPyP][UO2Cl4]2·6MeCN, a discrete dinuclear hydrogen-bonded complex. In one case, a neutral, hydrogen-bonded complex, Ce(NO3)3(MeOH)3(H2O)·TPyP·TCE·H2O, was formed which adopts a three-dimensional, self-penetrated variant of the face-centered cubic (fcc) network. These new structures represent hybrid organic-inorganic crystalline compounds in which the multidentate porphyrin units, having both hydrogen bonding, as well as coordination functionalities, are interlinked through the inorganic connectors into self-assembled three-dimensional architectures. This work shows the relative stability of noncovalently bound vs. coordination networks as well as the effective potential of the TPyP building block to construct supramolecular assemblies in the presence or absence of coordinating ions as linkers.


Original languageEnglish
Pages (from-to)3529-3542
JournalCrystal Growth & Design
Issue number6
Early online date19 Apr 2019
Publication statusPublished - 5 Jun 2019

    Research areas

  • Porphyrins, Coordination polymers, Topological analysis, Liquid-liquid diffusion, Hydrogen bonding

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates

    Matviitsuk, A., Greenhalgh, M. D., Taylor, J. E., Nguyen, X. B., Cordes, D. B., Slawin, A. M. Z., Lupton, D. W. & Smith, A. D., 23 Dec 2019, In : Organic Letters. Article ASAP

    Research output: Contribution to journalArticle

  2. Unexpected α,α'-difluoroethers from Ag(i)F and N-bromosuccinimide reactions of dibenzo[a,e]cyclooctatetraene

    Fang, Z., Gillatt, R. Z., Slawin, A. M. Z., Cordes, D. B., Carpenter-Warren, C. L. & O'Hagan, D., 11 Dec 2019, In : Chemical Communications. 55, 95, p. 14295-14298 4 p.

    Research output: Contribution to journalArticle

  3. Improving processability and efficiency of Resonant TADF emitters: a design strategy

    Hall, D., Madayanad Suresh, S., dos Santos, P. L., Duda, E., Bagnich, S., Pershin, A., Pachai Gounder, R., Cordes, D. B., Slawin, A. M. Z., Belijonne, D., Köhler, A., Samuel, I. D. W., Olivier, Y. & Zysman-Colman, E., 3 Dec 2019, In : Advanced Optical Materials. Early View, 1901627.

    Research output: Contribution to journalArticle

Related by journal

  1. Enhancement of electrical conductivity due to structural distortion from linear to nonlinear dicarboxylato-bridged Zn(II) 1D-coordination polymers

    Naskar, K., Sil, S., Sahu, N., Dutta, B., Slawin, A. M. Z., Ray, P. P. & Sinha, C., 1 May 2019, In : Crystal Growth & Design. 19, 5, p. 2632-2641 10 p.

    Research output: Contribution to journalArticle

  2. Evolution of anodic product from molybdenum metal in absolute ethanol and humidity sensing under ambient conditions

    Ni, C., Carolan, D., Hui, J., Rocks, C., Padmanaban, D., Ni, J., Xie, D., Fang, Z., Irvine, J., Maguire, P. & Mariotti, D., 4 Sep 2019, In : Crystal Growth & Design. 19, 9, p. 5249-5257 9 p.

    Research output: Contribution to journalArticle

  3. Formation mechanisms of ZnO spherulites and derivatives

    Connolly, B., Greer, H. F. & Zhou, W., 2 Jan 2019, In : Crystal Growth & Design. 19, 1, p. 249-257 9 p.

    Research output: Contribution to journalArticle

  4. The characteristics and biological relevance of inorganic amorphous calcium carbonate (ACC) precipitated from seawater

    Evans, D., Webb, P. B., Penkman, K., Kroger, R. & Allison, N., 7 Aug 2019, In : Crystal Growth & Design. 19, 8, p. 4300-4313

    Research output: Contribution to journalArticle

ID: 258758772