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Spectrally-Resolved Third-Harmonic Generation and Fundamental Role of O-H∙∙∙Cl Hydrogen Bonding in Oh, Td-Cobalt(II) Tetraphenylmethane-based Coordination Polymer

Abstract

The reaction of phosphonate-diester tetraphenylmethane-based tecton, tetrakis[4-(diethoxyphosphoryl)phenyl]methane, (L) with cobalt(II) chloride afforded a centrosymmetric coordination polymer (CP), [L∙2Co(H2O)42+∙2CoCl42-]n, 2-Cl, possessing simultaneously octahedral (Oh) and tetrahedral (Td) metal centers. This material served as a model compound for the demonstration of factors influencing the spectral dependence ofone of nonlinear optical (NLO) phenomena – the third-harmonic generation (THG). The spectrally-resolved THG (SR-THG) measurements in the range from 1125 to 1750 nm revealed that a maximum of THG response is obtained when the fundamental beam is around 1300 nm. The SR-THG study was combined with an analysis of self-absorption effects of pumping and of third-harmonic radiation; basing on those results we put forward a hypothesis that the THG action spectrum is influenced more by the ability of material to self-absorb the third harmonic rather than by the extent of self-absorption of the pumping radiation. Apart from investigations of NLO properties, we have explored coordination and particularly the supramolecular interactions that build up the 2-Cl CP. Despite tetrahedral, spatial shape of the ligand L, CP 2-Cl has a two-dimensional net. The structure was found to be strongly supported by O-H∙∙∙Cl hydrogen bonds, since each CoCl42- complex anion is an acceptor of eight of such interactions within distorted square grid layer of cobalt(II) ions. While coordination and hydrogen-bonded nets are both featuring sql topology when treated separately, the consideration of both of them as topological paths yields trinodal 4,4,6-connected net, described by point symbol (42.84)(45.6)2(46.66.83)2. SR-THG and structural studies of 2-Cl have been also supported by far- and mid-infrared spectroscopies, UV-Vis-NIR solid state absorption analysis, thermogravimetry and preliminary magnetic characterization.

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Publication details

The article was received on 26 Apr 2017, accepted on 14 Jun 2017 and first published on 14 Jun 2017


Article type: Paper
DOI: 10.1039/C7DT01518F
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Spectrally-Resolved Third-Harmonic Generation and Fundamental Role of O-H∙∙∙Cl Hydrogen Bonding in Oh, Td-Cobalt(II) Tetraphenylmethane-based Coordination Polymer

    J. K. Zaręba, J. Janczak, M. Samoc and M. Nyk, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01518F

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