Pronounced Magnetic Bistability in Highly Cooperative Mononuclear [Fe(Lnpdtz)2(NCX)2] Complexes.

Molecular materials that exhibit stimuli-responsive bistability are promising candidates for the development of molecular switches and sensors. We herein report on the coexistence of a wide thermal hysteretic spin crossover (SCO) effect and a thermally inducible metastable high-spin state at low temperatures achieved with the two new complexes [FeII(Lnpdtz)2(NCX)2] (X = S; Se), with Lnpdtz being (2-naphthyl-5-pyridyl-1,2,4-thiadiazole) and X = S (1) and Se (2). Pronounced π-π-stacking of the aromatic side residues of the ligands enables strong intermolecular interactions, leading to abrupt SCO properties and broad magnetic hysteresis of 10 K for X = S and 58 K for X = Se. In this paper, we also present the pressure-induced spin-state switching around 0.8 GPa. A pronounced thermally induced excited spin state trapping (TIESST effect) is observed for the highly cooperative SCO compounds, which was experimentally followed by low-temperature single crystal structure analysis (20 K) and temperature-dependent Mössbauer spectroscopy.

Substituent Effects on Photoinitiation Ability of Monoaminoanthraquinone-Based Photoinitiating Systems for Free Radical Photopolymerization under LEDs.

Three monoamino-substituted anthraquinone derivatives (AAQs), that is, 1-aminoanthraquinone (AAQ), 1-(methylamino)anthraquinone (MAAQ), and 1-(benzamido)anthraquinone (BAAQ), incorporated with various additives [e.g., triethanolamine (TEAOH) and phenacyl bromide (PhC(═O)CH2 Br)] are investigated for their roles as photoinitiating systems of free radical photopolymerization of (meth)acrylate monomers upon the exposure to UV to green LEDs. The AAQs-based photoinitiating systems, AAQ/TEAOH/PhC(═O)CH2 Br and BAAQ/TEAOH/PhC(═O)CH2 Br photoinitiators exhibit the highest efficiency for the free radical photopolymerization of DPGDA under the irradiation of blue LED and UV LED, respectively, which is consistent with the extent of overlap between their absorption spectra and the emission spectra of the LEDs. AAQ/TEAOH/PhC(═O)CH2 Br photoinitiator can also initiate the free radical photopolymerization of different (meth)acrylate monomers, with an efficiency dependent on the chemical structures of these monomers.

Photoinitiation Mechanism and Ability of Monoamino-Substituted Anthraquinone Derivatives as Cationic Photoinitiators of Polymerization under LEDs.

The design and development of photoinitiating systems applicable to UV or even visible light delivered from light-emitting diodes (LEDs) has been attracting increasing attention due to their great potential applications in various fields. Compared to the strategy of synthesizing novel compounds, the exploration of existing chemicals with interesting photochemical/photophysical properties for their usage as photoinitiators is more appealing and easily commercialized. Nevertheless, a number of compounds such as monoamino-substituted anthraquinone derivatives, which are intensively investigated for their photophysical and photochemical properties, have seldom been studied for their roles as photoinitiators under LED irradiation. Herein, three monoamino-substituted anthraquinone derivatives, that is, 1-aminoanthraquinone, 1-(methylamino)anthraquinone and 1-(benzamido)anthraquinone, are studied for their potential as photoinitiators. The photoinitiation mechanism of these monoamino-substituted anthraquinone derivatives, when combined with iodonium salt, is first clarified using computational quantum chemistry, fluorescence, steady-state photolysis, and electron spin resonance spin-trapping techniques. Then, their photoinitiation ability for the cationic photopolymerization of epoxide and divinyl ether monomers is also investigated.

Quantification of the thermodynamic effects of the low-spin - high-spin interaction in molecular crystals of a mononuclear iron(II) spin crossover complex.

A method is proposed to estimate the energetic and entropic effects of spins of neighbouring molecules on the spin transition of a mononuclear spin crossover (SCO) complex in a molecular crystal. Density functional theory (DFT) methods have been used to model the SCO material [FeII(Lnpdtz)2(NCS)2] (Lnpdtz = 2-naphthyl-5-pyridyl-1,2,4-thiadiazole) exhibiting numerous π-π interactions using a 2D arrangement of 15 molecules. The modelling considers only the effects in the crystallographical ac plane with a particularly pronounced stacking but paves the way for future work with 3D arrangements which are computational much more costly. It involves the optimisation and normal mode calculation of the molecules in a rigid matrix of both low-spin (LS) and high-spin (HS) neighbours. This procedure has been used to calculate the previously defined cooperativity parameter Hcoop (S. Rackwitz, W. Klopper, V. Schünemann and J. A. Wolny, Phys. Chem. Chem. Phys., 2013, 15, 15450). For [FeII(Lnpdtz)2(NCS)] we obtain Hcoop = 11 kJ mol-1, a value which is comparable to those found for 3D polynuclear spin crossover materials. A normal mode analysis of the optimised centrally located molecule indicates that the vibrational entropy of the spin transition is somewhat higher (5 J K-1 mol-1) for the LS to HS transition in the LS matrix than in the HS one. The calculations show that the interactions with the neighbours influence the low-frequency modes with wave numbers <65-70 cm-1. These cause the main difference in the vibrational entropy of the spin transition for the vicinity of high- and low-spin molecules. Furthermore, a deformation of the coordination sphere of the central molecule is observed when the spins of the surrounding centres are switched. This deformation is accompanied by a change in the equatorial Fe-N bond lengths.