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Issue 29, 2017
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Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(II) tetraphenylmethane-based coordination polymers

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Abstract

The reaction of a 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 of one of the 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 the self-absorption effects of pumping and of third-harmonic radiation; based on these results, we put forward a hypothesis that the THG action spectrum is influenced more by the ability of the 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 the 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 a distorted square grid layer of cobalt(II) ions. While coordination and hydrogen-bonded nets are both featuring the sql topology when treated separately, the consideration of both of them as topological paths yields a trinodal 4,4,6-connected net, described by the 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 spectroscopy, UV-Vis-NIR solid state absorption analysis, thermogravimetry and preliminary magnetic characterization.

Graphical abstract: Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(ii) tetraphenylmethane-based coordination polymers

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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., 2017,46, 9349-9357
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    Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(II) tetraphenylmethane-based coordination polymers

    J. K. Zaręba, J. Janczak, M. Samoć and M. Nyk, Dalton Trans., 2017, 46, 9349
    DOI: 10.1039/C7DT01518F

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