Tunable third-order nonlinear optical effect via modifying Ti₄(embonate)₆ cage-based ionic pairs

Abstract

Benefiting from the strong inherent π-conjugation properties, the integration of Ti4L6 (L = embonate) cages and various N, N-chelated transition-metal cations into tightly packed structures accurately lead to the high-performance...

Optical limiting effects of 1,10-phenanthroline functionalized heterometallic Sn–Ti oxo clusters with distinct π⋯π interactions

“…These results show that the difference in the light absorption behavior among the three structures may be attributed to the strength of π⋯π interactions, which is consistent with the literature reports. 17,35…”

“…It is widely acknowledged that the presence of conjugated organic molecules and the strength of π⋯π interactions in crystal structures can have a direct impact on the OL effects of materials. 35,36 Based on these considerations, we employed 1,10-phenanthroline as an organic ligand due to its highly conjugated π electron system and strong coordination ability with Sn and Ti atoms. Thereupon, three heterometallic Sn–Ti oxo clusters modified by 1,10-phenanthroline, including [Sn II 2 Ti IV 12 (μ 3 -O) 6 (μ 2 -O) 12 (phen) 8 (Pr) 10 Cl 2 ]·(Sn II Cl 3 ) 2 ·(Pr) 2 ·(CH 3 CN) 2 ( TOC-61 , HPr = propionic acid; phen = 1,10-phenanthroline), [Sn II 2 Ti IV 12 (μ 3 -O) 8 (μ 2 -O) 10 (phen) 8 (IPA) 4 (Pr) 8 Cl 2 ]·(Sn II Cl 3 ) 2 ( TOC-62 , HIPA = isopropanol), and [Sn II 6 Ti IV 14 (μ 3 -O) 9 (μ 2 -O) 14 (phen) 6 (Pr) 14 Cl 6 ]·Sn II Cl 3 ·Pr ( TOC-63 ), were successfully assembled under similar reaction conditions (Fig.…”

Combining Ti 4(embonate) 6 cages and [Pb 4(OH) 4] 4+ clusters for enhanced third-order nonlinear optical property

“…In our previous work, we developed a powerful titaniumorganic tetrahedral cage [23] (PTC-101: [(Me 2 NH 2 ) 8 (Ti 4 L 6 )]•G; L = embonate; G = guest), which has proven to be an excellent building block owing to its abundance of oxygen coordination sites as well as high solubility and stability in solvents, providing an intriguing stepwise assembly function with transition-metal and lanthanidemetal ions [24][25][26][27][28][29]. Here, using a stable Ti 4 L 6 cage to assemble with Pb 2+ ions, a novel cage-cluster-based framework was readily prepared, namely, {(NH 4 ) 4 [Pb 4 (μ 3 -OH) 4 (Ti 4 L 6 )]}•guest (PTC-290).…”

Designing Cage-Supported Cluster-Organic Framework for Highly Efficient Optical Limiting

“…The third-order nonlinear optical (NLO) materials have been widely applied in optical switching, logic devices, optical limiting, data storage, image transmission, and optical computing. − In the past few decades, a variety of elaborately designed materials have been developed for third-order NLO, including carbon nanodots, semiconductor quantum dots, black phosphorus, conjugated organic molecules (such as phthalocyanines and porphyrins) or polymers, − metal clusters, , metal-oxo clusters, , metal–organic frameworks (MOFs), − etc. Recently, we discovered that metal–organic cages (MOCs) with unique interior cavities are also promising third-order NLO materials. − Thus, a simple idea is to combine three structural types (e.g., MOCs, metal-oxo clusters, and MOFs) into one system. Considering both MOCs and metal-oxo clusters may be the building blocks of MOFs, − such an idea is applicable and may be a new construction mode for third-order NLO materials.…”