Porphyrins and metalloporphyrins as field-responsive materials
{\it Part I}. {\it Metalloporphyrin coordination polymers}. One-dimensional coordination polymers of metalloporphyrins with non-symmetric bridging ligands have been synthesized as candidates for molecular ferroelectric materials. These include the iron(II) porphyrinate polymer: \lbrack Fe$\sp{\rm II}$(TPP)(pyCN)\rbrack$\sb\infty$ (where TPP = 5,10,15,20-tetraphenylporphyrinate(2$-$); pyCn = 4-cyanopyridine); iron(III) porphyrinate polymers: \lbrack Fe$\sp{\rm III}$(TPP)(4-MeIm)\rbrack$\sb\infty$, \lbrack Fe$\sp{\rm III}$(TPP)(4-PhIm)\rbrack$\sb\infty$, \lbrack Fe$\sp{\rm III}$(TPP)(pyCO$\sb2$)\rbrack$\sb\infty$, \lbrack Fe$\sp{\rm III}$(TPP)(OpyCO$\sb2$)\rbrack$\sb\infty$, and \lbrack Fe$\sp{\rm III}$(TPP)(ImPhO)\rbrack$\sb\infty$ (where 4-MeIm = 4-methylimidazolate; 4-PhIm = 4-phenylimidazolate; pyCO$\sb2\sp-$ = pyridine-4-carboxylate; OpyCO$\sb2\sp-$ = pyridine-4-carboxylate N-oxide; ImPhO$\sp-$ = 4-(imidazol-1-yl)phenoxide); tin(IV) porphyrinate polymers: \lbrack Sn$\sp{\rm IV}$(TPP)(ntp)\rbrack$\sb\infty$ and \lbrack Sn$\sp{\rm IV}$(TPP)(cnp)\rbrack$\sb\infty$ (where ntp = nitroterephthalate; cnp = 4-carboxyl-2-nitrophenoxide). The single-crystal X-ray structures were solved for \lbrack Fe$\sp{\rm II}$(TPP)(pyCN)\rbrack$\sb\infty$, \lbrack Fe$\sp{\rm III}$(TPP)(pyCO$\sb2$)\rbrack$\sb\infty$, \lbrack Fe$\sp{\rm III}$(TPP)(OpyCO$\sb2$)\rbrack$\sb\infty$, and Fe$\sp{\rm III}$(TPP)(ImPhO)\rbrack$\sb\infty$. The chain alignment of the bridging ligand is disordered in \lbrack Fe$\sp{\rm II}$(TPP)(pyCN)\rbrack$\sb\infty$, anti-parallel in \lbrack Fe$\sp{\rm III}$(TPP)(pyCO$\sb2$)\rbrack$\sb\infty$ and \lbrack Fe$\sp{\rm III}$(TPP)(OpyCO$\sb2$)\rbrack$\sb\infty$, but polar in \lbrack Fe$\sp{\rm III}$(TPP)(ImPhO)\rbrack$\sb\infty$. \lbrack Fe$\sp{\rm III}$(TPP)(ImPhO)\rbrack$\sb\infty$ crystallizes in a non-centrosymmetric space group, $Pna2\sb1$.
Chemistry, Inorganic, Chemistry, Organic
University of Illinois - Urbana-Champaign
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University of Illinois at Urbana-Champaign