Structure and third-order nonlinear optical properties of the two-dimensional Co^IIcoordination polymer [Co(1,2-BIB)(PA)]_n{1,2-BIB is 1,2-bis[(1H-imidazol-1-yl)methyl]benzene and H₂PA is phthalic acid}

Abstract

The design of nonlinear optical (NLO) materials with large NLO responses has been a challenge for materials scientists and chemists. Recently, organic polymers have received attention regarding their NLO properties and fast nonlinear response, and clusters involving delocalized dπ-pπ systems and conjugated dπ-pπ systems are expected to be a new class of NLO materials. Metal-organic coordination polymers combine the advantages of the organic and inorganic species. Thus far, tuning the third-order NLO properties of these materials has been a significant challenge. A two-dimensional coordination polymer, namely poly[(μ-benzene-1,2-dicarboxylato-κO,O:O){μ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κN:N}cobalt(II)], [Co(CHO)(CHN)], was synthesized by hydrothermal methods. In the structure, the Co ion is pentacoordinated by two N atoms from two different 1,2-bis[(1H-imidazol-1-yl)methyl]benzene (1,2-BIB) ligands and three O atoms from two symmetry-related benzene-1,2-dicarboxylate (isophthalate, PA) anions. The pentacoordinated Co ions are linked by PA ligands to form a chain structure parallel to the c axis. Adjacent chains are further connected by 1,2-BIB ligands to produce a two-dimensional layered structure. The compound exhibits strong third-order nonlinear absorption and nonlinear refraction effects as a thin film. The third-order susceptibility χ is calculated to be 1.07 × 10 esu, which is much larger than the values found for pure inorganic semiconductors and some polymers.

Photofunctional metal-organic framework thin films for sensing, catalysis and device fabrication

“…Two photon absorption and third harmonic generation are both third order processes [185]. A few examples of third order NLO have been conducted on films supported on quartz, obtained upon evaporation of MOF suspensions in ethanol [186,187]. Multiphoton absorption of MOF nanoparticles has possible application in bioimaging and photo-therapies, employing infrared radiation [180].…”