Molecular design and theoretical investigation into one-and two-photon absorption properties of two

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We have theoretically investigated two series of cyclometalated Pt(Ⅱ) complexes,a series [Pt(C,N,N) Cl] and b series [Pt(C,N,Npyrazolyl) Cl].The geometrical and electronic structures are calculated at the ECP60MWB//6-31G*(H,C,Cl,N,S) basis set level using DFT method;one-photon absorption(OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption(TPA) properties are obtained with the ZINDO/SOS method.The resonance integrals parameters(βsp and βd) for Pt are adjusted to -1 and -28.5 eV,respectively,to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results.The calculated results indicate the molecule 2b([Pt(Cnaphthyl,N,Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because(i) the TPA properties of b series are more outstanding in IR wavelength range,the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination(e.g.,dimerization) and chemical interactions;(ii) when C is Cnaphthyl in the C,N,N ligand of cyclometalated Pt(Ⅱ) complexes,the molecules have the best conjugation effect and the best TPA properties. We have theoretically investigated two series of cyclometalated Pt (Ⅱ) complexes, a series [Pt (C, N, N) Cl] and b series [Pt (C, N, Npyrazolyl) Cl] the ECP60MWB // 6-31G * (H, C, Cl, N, S) basis set level using DFT method; one-photon absorption (OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption (TPA ) properties are obtained with the ZINDO / SOS method. The resonance integrals parameters (βsp and βd) for Pt are adjusted to -1 and -28.5 eV, respectively, to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results The calculated results indicate that the molecule 2b ([Pt (Cnaphthyl, N, Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because (i) the TPA properties of b series are more outstanding in IR wavelength range, the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination (eg, d (ii) when C is Cnaphthyl in the C, N, N ligand of cyclometalated Pt (II) complexes, the molecule has the best conjugation effect and the best TPA properties.
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