The diversity of Zn(ii) coordination networks composed of multi-interactive ligand TPHAP⁻via weak intermolecular interaction

Abstract

Seven types of different Zn(TPHAP) coordination networks were prepared thanks to the excellent multi-interactivity of TPHAP via weak intermolecular interactions.

Do Anionic π Molecules Aggregate in Solution? A Case Study with Multi‐interactive Ligands and Network Formation

“…Interestingly, the 0.40 m m solution (green line) showed a significant intensity increase at 300 and 360 nm with a slight shoulder at 400 nm, which can be assigned to an H‐aggregation dimer for the former and a J‐aggregation dimer for the latter with a J‐type higher oligomer, according to the exciton theory . In fact, we have also revealed that K + TPHAP − tends to form the salt‐bridging dimer as indicated by CSI‐MS measurements . At 2.0 m m (light blue line), the peak at 360 nm almost completely disappeared and the intensities at 380 nm and 400 nm increased.…”

“…In fact, we have demonstrated that TPHAP − can trap the kinetic states of PCNs . The multi‐interactivity of TPHAP − produced various metastable networks by changing only solvents or additives in the reactions . These results indicate that the solution states of TPHAP − , i.e., monomer or aggregation, greatly affect the morphological features of the networks.…”

“…To understand the origin of the absorption at longest wavelength, we performed TD‐DFT calculations at the MPW1PW91/6‐31G+(d,p) level of theory (see Table S5 and the relevant data in the Supporting Information) using K + TPHAP − as a model because, even in polar solvent such as MeOH, K + TPHAP − exists not as solvent‐separated ion pair but as a contact ion pair, as indicated by cold‐spray ionization‐mass spectrometry (CSI‐MS; see Figure S3) . In fact, the absorption at longest wavelength can be reproduced by calculations using a K + TPHAP − model rather than a free TPHAP − model (Table S6 and relevant data in the Supporting Information).…”

“…[19] In fact, we have also revealed that K + TPHAP À tends to form the saltbridging dimer as indicated by CSI-MS measurements. [13] At 2.0 mm (light blue line), the peak at 360 nm almost completely disappeared and the intensities at 380 nm and 400 nm increased. At 10 mm (blue line), the intensity at 400 nm further increased and the peak at 380 nm disappeared.A t2 5mm (purple line), the spectrum broadened over ar elativelyw ide range with three shouldersa t4 00, 420, and 430 nm.…”

“…[12] The multiinteractivity of TPHAP À produced various metastable networks by changing only solvents or additives in the reactions. [13] Theser esultsi ndicatet hat the solution states of TPHAP À ,i .e., monomer or aggregation, greatly affect the morphological features of the networks. These interactive behaviors prompted us to investigate an aggregation of this anionic p molecule.…”