N-Heteroacenes as an Organic Gain Medium for Room-Temperature Masers.

The development of future quantum devices such as the maser, i.e., the microwave analog of the laser, could be well-served by the exploration of chemically tunable organic materials. Current iterations of room-temperature organic solid-state masers are composed of an inert host material that is doped with a spin-active molecule. In this work, we systematically modulated the structure of three nitrogen-substituted tetracene derivatives to augment their photoexcited spin dynamics and then evaluated their potential as novel maser gain media by optical, computational, and electronic paramagnetic resonance (EPR) spectroscopy. To facilitate these investigations, we adopted an organic glass former, 1,3,5-tri(1-naphthyl)benzene to act as a universal host. These chemical modifications impacted the rates of intersystem crossing, triplet spin polarization, triplet decay, and spin-lattice relaxation, leading to significant consequences on the conditions required to surpass the maser threshold.

Move Aside Pentacene: Diazapentacene-Doped para-Terphenyl, a Zero-Field Room-Temperature Maser with Strong Coupling for Cavity Quantum Electrodynamics.

Masers can deliver ultralow-noise amplification of microwave signals in medical imaging and deep-space communication, with recent research being rekindled through the discovery of gain media operating at room-temperature, eschewing bulky cryogenics that hindered their use. This work shows the discovery of 6,13-diazapentacene doped in para-terphenyl (DAP:PTP) as a maser gain medium that can operate at room-temperature, without an external magnetic field. With a maser output power of -10 dBm, it is on par with pentacene-doped para-terphenyl in masing power, while possessing compelling advantages such as faster amplification startup times, being pumped by longer wavelength light at 620 nm and greater chemical stability from nitrogen groups. Furthermore, the maser bursts from DAP:PTP allow one to reach the strong coupling regime for cavity quantum electrodynamics, with a high cooperativity of 182. The optical and microwave spin dynamics of DAP:PTP are studied in order to evaluate its capabilities as a maser gain medium, where it features fast intersystem crossing and an advantageously higher triplet quantum yield. The results pave the way for the future discovery of similar maser materials and help designate them as promising candidates for quantum sensors, optoelectronic devices and the study of cavity quantum electrodynamic effects at room-temperature.

Exceptionally high temperature spin crossover in amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complex revealed by variable temperature Raman spectroscopy and single crystal X-ray diffraction.

The synthesis of a novel amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine-4-carboxamide ligand (bppCONH2) is described. The complex salts [Fe(bppCONH2)2](BF4)2 and [Fe(bppCONH2)2](ClO4)2 were synthesised and characterised by SQUID magnetometry, differential scanning calorimetry, variable temperature Raman spectroscopy and single crystal X-ray diffraction. DSC measurements of [Fe(bppCONH2)2](BF4)2 indicate a spin-crossover (SCO) transition with T↑ at 481 K and T↓ at 461 K, showing a 20 K hysteresis. DSC for the perchlorate salt shows an SCO transition with T↑ at 459 K and T↓ at 445 K with a 14 K hysteresis. For the BF4- salt analysis of low and high-spin state crystal structures at 101, 290 and 500 K, suggest stabilisation of the low spin state due to the formation of 1D hydrogen-bonded cationic chains. Variable temperature Raman studies of the BF4 salt support the presence of a high temperature SCO. It is speculated that the presence of hysteresis may be attributed to differences in the inter-molecular hydrogen bonding in the low spin and high spin states.

Above room temperature spin crossover in thioamide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complexes.

This work describes the synthesis of two novel functionalised 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands, namely 2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNH2) and N-methyl-2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNHMe). The corresponding solvated or non-solvated Fe(ii) salts, [Fe(bppCSNH2)2]X2 and [Fe(bppCSNHMe)2]X2 (X = BF4- or ClO4-) were synthesised and their properties measured by SQUID magnetometry, Evans NMR, differential scanning calorimetry and single crystal X-ray diffraction. In the solid state [Fe(bppCSNH2)2]2+ salts persist in the low spin state below 350 K. The structure of [Fe(bppCSNH2)2](BF4)2·2MeNO2 shows a network of intermolecular interactions responsible for the low spin state stabilisation, relative to the prototypical [Fe(bpp)2]2+ spin crossover (SCO) salts. By contrast the complexes of bppCSNHMe both display abrupt SCO above 300 K. [Fe(bppCSNHMe)2](BF4)2·MeNO2 requires solvent loss before SCO can be observed centred at 332 K. The non-solvated [Fe(bppCSNHMe)2](ClO4)2 shows SCO centred at 325 K. Analysis of solvated and non-solvated crystal structures suggests that cooperativity is facilitated by thioamide-group interactions with neighbouring pyrazolyl and pyridyl moieties.