Optical Signal Modulation in Photonic Waveguiding Heteroarchitectures with Continuously Variable Visible‐To‐Near‐Infrared Emission Color

Abstract

Photonic circuit systems based on optical waveguiding heteroarchitectures have attracted considerable interest owing to their potential to overcome the speed limitation in electronic circuits by modulating the optical signal at the micro‐ or nanoscale. However, controlling the parameters, including the wavelength and polarization of the light outcoupling, as well as the sequence among different building blocks, remains a key issue. Herein, supramolecular heteroarchitectures made by phosphorescent organometallic complexes of Pt, Pd, Cu, and Au are applied as photonic logic gates that show continuously variable emission colors from 475 to 810 nm, low waveguide losses down to 0.0077 dB µm−1, and remarkable excitation‐light polarization‐dependent photoluminescence with anisotropy ratios up to 0.68. The sequences among Pt, Pd, Au, and Cu building blocks in the heteroarchitectures are controlled by living supramolecular polymerization or crystallization‐driven self‐assembly synthetic approaches. The results indicate the prospects for using organometallic complexes and supramolecular synthetic approaches to prepare photonic circuit systems with tunable emission color and controllable sequences among different blocks that achieve modulation of the optical signal in the visible‐to‐near‐infrared spectral region.

Multistimuli-responsive behavior of a phosphorescent Cu3pyrazolate3complex for luminescent logic gates and encrypted information transformation

“…Rapid developments in molecular logic gates have been achieved since the emergence of the first AND molecular logical gate proposed by Silva in the 1993, 19 due to their potential applications in disease diagnostics and therapy, 22 chemical sensing, 23 microfluidic devices, 24 photonic circuit systems, 25 etc . The input signals of molecular logic gates are always regarded as external stimuli, such as pH, various ions, temperature, viscosity and many others, 19 thereby multi-responsive materials seem to be ideal candidates for molecular logic gates.…”

“…[19][20][21] To date, in order to better meet the complicated requirements of real-world applications, the focus of development of stimuli-responsive materials has been transferring to multi-responsive luminescent materials although they remain much less investigated relative to the mono-responsive ones. 4,7 Rapid developments in molecular logic gates have been achieved since the emergence of the first AND molecular logical gate proposed by Silva in the 1993, 19 due to their potential applications in disease diagnostics and therapy, 22 chemical sensing, 23 microfluidic devices, 24 photonic circuit systems, 25 etc. The input signals of molecular logic gates are always regarded as external stimuli, such as pH, various ions, temperature, viscosity and many others, 19 thereby multiresponsive materials seem to be ideal candidates for molecular logic gates.…”

Aggregation of phosphorescent Pd(ii) and Pt(ii) complexes with lipophilic counter-anions in non-polar solvents

“…31 Recently, the construction of metallophilic interactions has emerged as a new strategy for creating phosphorescent Pd(II) complexes and aggregates. [32][33][34][35][36][37] In 2018, Che and co-workers reported a tridentate cyclometallated Pd(II) isocyanide complex with live aggregation properties in a nucleation-elongation manner, achieving effective phosphorescent MMLCT emission enabled by metallophilic Pd(II)⋯Pd(II) interactions. 32 In 2020, Che et al reported on their successful manipulation of mixed aggregates of a series of tridentate Pd(II) and Pt(II) complexes, under the kinetic control of metallophilic interactions, which showed tuneable and amplified MMLCT phosphorescence.…”

“…33 Moreover, Che et al have made a recent breakthrough in the advancement of photonic logic gates by utilizing phosphorescent tridentate C^N^N cyclometallated Pt( ii )/Pd( ii ) isocyanide complexes and Au( i )–Au( i )/Cu( i ) double salts, as fundamental building blocks to create precisely controlled mixed aggregates driven by metallophilic interactions. 34 In 2018, Lu and co-workers also reported a stable tridentate cyclometallated Pd( ii ) N-heterocyclic allenylidene complex forming highly efficient phosphorescent aggregates in nonpolar solvents with absolute MMLCT characteristics. 35 With multidentate arylacetylide ligands, highly phosphorescent organopalladium( ii ) and helically chiral Pd( ii ) complexes as circularly polarized molecular phosphors in room-temperature fluid solutions, containing intramolecular Pd( ii )⋯Pd( ii ) metallophilicity, were achieved by Lu et al in 2019 and 2021, respectively.…”