Abstract
The electronic and nonlinear optical (NLO) properties of octaphyrin derivatives were studied by employing the DFT/TDFT at CAM-B3LYP/6-311++G (2d, 2p) level of the theory. Thiophene, phenyl, methyl and cyano moieties were substituted on the molecular framework of octaphyrin core, in order to observe the change in optoelectronic and nonlinear response of these systems. The frontier molecular orbital studies and values of electron affinity reveals that the studied compounds are stable against the oxygen and moisture present in air. The calculated ionization energies, adiabatic electron affinity and reorganization energy values indicate that octaphyrin derivatives can be employed as effective n-type material for Organic Light Emitting Diodes (OLEDs). This character shows an enhancement with the introduction of an electron withdrawing group in the octaphyrin framework. The polarizability and hyperpolarizability values of octaphyrin derivatives demonstrate that they are good candidates for NLO devices. The nonlinear response of these systems shows enhancement on the introduction of electron donating groups on octaphyrin moiety. However, these claims needs further experimental verification.
Highlights
INTRODUCTIONThe discovery of sapphyrins and expanded porphyrins have attracted the interest of researchers attributed to their diverse applications in materials science (Sprutta and Latos-Grazynski, 2001; Flemming and Dolphin, 2002; Pushpan et al, 2002; Silva et al, 2002a,b; Cavaleiro et al, 2003; Hata et al, 2006; Tanaka and Osuka, 2016)
In case of octaphyrin derivatives (OP)-II and OP-III the methyl and the phenyl groups present on C24 and C32 are oriented toward the center resulting in hyperbolic nonlinearity in the derivatives respectively
Calculated properties like electron affinity and ionization energy values show that all these derivatives are stable toward oxygen and water in the air
Summary
The discovery of sapphyrins and expanded porphyrins have attracted the interest of researchers attributed to their diverse applications in materials science (Sprutta and Latos-Grazynski, 2001; Flemming and Dolphin, 2002; Pushpan et al, 2002; Silva et al, 2002a,b; Cavaleiro et al, 2003; Hata et al, 2006; Tanaka and Osuka, 2016). Expanded porphyrins are macrocyclic compounds containing five-membered heterocyclic units (like pyrrole, furan, or thiophene) linked together, either directly or through spacers with internal ring pathway contains at least 17 atoms (Sprutta and Latos-Grazynski, 2001; Flemming and Dolphin, 2002; Pushpan et al, 2002; Silva et al, 2002a,b; Hata et al, 2006) Their distinctive physical and structural properties have found applications in nonlinear optical (NLO) materials (Marder et al, 1997; Zhou et al, 2002; Ahn et al, 2005; Rath et al, 2005a; Misra et al, 2006), photosensitizers for photodynamic therapy (PDT) (Harriman et al, 1989; Maiya et al, 1989), transition or rare earth metal ion chelates, cation and anion receptors (Shionoya et al, 1992; Jasat and Dolphin, 1997; Sessler et al, 2000a,b; Sessler and Davis, 2001; Chandrashekar and Venkatraman, 2003), magnetic resonance imaging (MRI) contrasting agents (Charrière et al, 1993; Weghorn et al, 1996; Werner et al, 1999) and a tool for accessing presently unknown higher aromatic systems. We have calculated the second-order hyperpolarizability of the octaphyrin derivatives, in order to conclude their appropriate NLO response
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