Electronic functionality of Gd-bisphthalocyanine: Charge carrier concentration, charge mobility, and influence of local magnetic field

Lanthanide bisphthalocyanine single-molecule magnets: A DFT survey of their geometries and electronic properties from lanthanum to lutetium

“…Given the nanometer-sized dimensions of LnPc 2 (the width of a single unsubstituted Pc ligand is about 1.5 nm) and their rather high molecular weight of >1000 Da, a natural choice of the computational methodology is density functional theory (DFT). Indeed, there is a number of studies, which employed pure and hybrid DFT functionals to study LnPc 2 systems [3,[26][27][28][29][30][31][32][33][34][35], though it does not seem to be particularly large. Here it is appropriate to make the following important observations.…”

“…First, none of the published studies comprises the complete lanthanide series, from La to Lu. Instead, each study is limited to only one [26,[28][29][30][31][32]34,35], two [33] or at best three [27] representative LnPc 2 species, as can be exemplified by La [26,32], Eu [27], Gd [30], Tb [29,[33][34][35], Dy [27,33], and Lu [3,27,28,31] derivatives. La with its totally empty [26,32] and Lu with its totally filled 4f orbitals [3,27,28,31] can be considered as the 'easiest' central atoms and, in total, less than half of the Ln series was addressed.…”

Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

“…These are the high charge carrier mobility, p‐channel, n‐channel, and ambipolar charge transport associated with the tunable HOMO and LUMO energy levels, the electron‐donor ability favoring photoinduced electron transfer (PET), the strong light absorption from the ultraviolet to the near‐infrared (IR) region, and the high reactivity of axial positions in the molecule. Metalloporphyrins (MPs) are studied and applied ascatalysts, [ 4–8 ] , chemical probes for ions, ion pairs, volatile organic compounds (VOCs), nitroaromatic compounds, gases, reactive oxygen species, [ 9 ] optical chemosensors, [ 10–16 ] semiconductors, [ 17–21 ] functional dyes for organic solar cells, [ 19,22–24 ] and photodynamic therapy. [ 19,25,26 ] Porphyrin/phthalocyanine derivatives of both the paramagnetic ions of 3 d elements and rare earth element (REE) were widely studied as single‐molecule magnets (SMMs) at the temperatures close to 0 K. [ 27–32 ] The derivatives displaying the Curie–Weiss behavior above the Curie temperature were studied as materials with a magnetocaloric effect (MCE) at the temperature close to room that is far from the temperature of the magnetic phase transition.…”

Hydrogen Bond-Mediated Conjugates Involving Lanthanide Diphthalocyanines and Trifluoroacetic Acid (Lnpc2@TFA): Structure, Photoactivity, and Stability

“…These include essentially modern electronics, optoelectronics, and catalytic applications. The peculiar molecular system consisting of a trivalent lanthanide (Ln) ion coordinated by two Pc macrocycles ( Figure 1 ) renders the LnPc 2 semiconductors display a considerably smaller energy bandgap and hence much better electrical conductivity and higher charge mobility compared with typical metallophthalocyanines (e.g., CuPc, ZnPc) [ 3 , 4 ]. This is considered crucial for intermolecular charge transfer in film integrated circuits, catalytic systems, and photoactive composites.…”