Photonic Applications Research Articles

Exploring the influence of sudan IV Azo dye on the structural, optical, and dispersion characteristics of PVA/Su-IV composites

Flexible polymeric film composites consisting of polyvinyl alcohol (PVA) and Sudan IV azo dye (Su-IV) were synthesized using a casting method. Despite the known optical properties of PVA and azo dyes individually, the combined effects of Su-IV doping in PVA on the material’s optical and nonlinear optical properties have not been thoroughly investigated. This study addresses this gap by exploring the interactions between PVA and Su-IV at various doping concentrations (0.1–0.8 wt%) and their subsequent impact on the material’s structural and optical characteristics. Fourier transform infrared (FTIR) spectroscopy was employed to identify distinct vibrational groups within the composites, revealing that the incorporation of Su-IV induced random deviations in most absorption intensities compared to pristine PVA. Notably, new peaks at 519 and 444 cm−1 emerged, intensifying with increasing Su-IV concentrations, indicating significant interactions between the composite constituents. The optical properties were analyzed through transmittance and reflectance measurements, which uncovered new absorption peaks at 518 and 357 nm in PVA/Su-IV composites. These peaks correspond to electronic energy transitions of 2.4 and 3.6 eV, respectively, and their intensities increased with higher Su-IV content. Additionally, the indirect and direct bandgaps were decreased as Su-IV concentrations increased. The refractive index (n) analysis showed typical dispersion behavior between 850 and 2500 nm, aligning with the Wemple-DiDomenico (WDD) model. Furthermore, the oscillator parameters were calculated. Also, the nonlinear optical susceptibility (χ(3)) was boosted from 4.19 × 10−6 for pure PVA to 3.60 × 10−4 for the sample with 0.8 wt% Su-IV. The nonlinear refractive index (n2) was also measured at 8.55 × 10−2 for the doped sample. These findings demonstrate the potential of PVA/Su-IV composites for applications in nonlinear optics and photonics.

DFT insights into the nonlinear optical properties of azulene-stilbene dyads for photonics and optoelectronics

The present study aims to investigate the nonlinear optical characteristics of a series of azulene-stilbene chromophores through the utilization of density functional theory (DFT). Various acceptor substitution techniques were used to enhance first, second, and third order static and dynamic polarizabilities of the parent azulene-stilbene dyad (AS). The natural transition orbitals and UV-Visible absorption spectra were analyzed using time dependent-density functional theory (TD-DFT). Theoretical computations were performed to analyze the structural, electronic, and charge transfer properties of all designed compounds. The energy gap separating the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the designed moieties was observed to decrease in the new compounds compared to the parent compound. Analysis of the nonlinear optical (NLO) data among the designed compounds (AS1-AS10) revealed that AS2, AS3, AS4, and AS10 exhibit promising second and third order NLO characteristics, with AS6 exhibits suitability as a second order NLO material and AS8 and AS9 display third order NLO responses. The computed static and dynamic NLO parameters and maximum absorption wavelength closely match the experimentally reported data in the literature, suggesting these derivatives are excellent candidates for photonic and optoelectronic applications in the future.

Bio‐Inspired Cellulose Composites With Multicolor Separation via Electro‐Thermal and Magneto‐Thermal Techniques for Multifunctional Applications

AbstractBiomimetic optical devices based on cellulose nanocrystals with tunable structural colors have received significant attention recently. However, the limited ability to control multicolor separation beyond simple single‐color modulation restricts its practical applications. Here, a diversified multicolor separation strategy for the cholesteric phase cellulose composite (CPCC) is presented. The CPCC is prepared by integrating a high‐concentration self‐assembled hydroxypropyl cellulose with a cross‐linked poly(acrylic acid‐acrylamide) (P(AA‐AM)) network. By adjusting the cross‐linking degree of P(AA‐AM) in CPCC, Thermally induced multicolor separation is achieved from a homochromatic state at room temperature to multicolor patterned display at elevated temperatures. Furthermore, by utilizing the electric heating effect of conductive carbon oil, the multicolor separation under low voltage is achieved, and based on this, pixelated electro‐thermochromic displays are developed. Additionally, magneto‐thermal multicolor separation induced by introducing FeNi3 nanoparticles is investigated with efficient magnetic induction heating ability into CPCC. The multicolor separation effect is further improved by pixelated distribution of FeNi3 nanoparticles and adjusting the concentration of FeNi3 in each pixel. Finally, thermochromism, electro‐thermochromic, and magneto‐thermochromic functionalities are integrated into the CPCC, achieving advanced multilevel information encryption. This multilevel approach of controlling multicolor separation significantly enhances the functionality of nanocellulose in various potential photonic applications.

Spontaneous parametric downconversion photon pair generation in small footprint X-cut periodically poled lithium niobate micro-resonator.

Spontaneous parametric downconversion (SPDC) has been crucial for producing non-classical light, such as correlated photon pairs and squeezed states, essential for optical quantum technologies. Recently, thin-film lithium niobate (TFLN)-based devices have enabled high-performance SPDC in on-chip integrated photonic platforms. Here, we developed an X-cut periodically poled lithium niobate (PPLN) racetrack micro-resonator with a compact footprint and demonstrated bright SPDC photon pair generation characterized by distinct resonances and high extraction efficiency. We separately assessed the internal and loaded photon pair generation rates, measuring them at 4.525 MHz/µW and 62.73 kHz/µW, respectively. Our platform is integrated with maturing electro-/thermo-optic TFLN circuit elements and has meaningful potential for advancing active quantum photonic applications.

Ultra-high endurance silicon photonic memory using vanadium dioxide

Silicon photonics arises as a viable solution to address the stringent resource demands of emergent technologies, such as neural networks. Within this framework, photonic memories are fundamental building blocks of photonic integrated circuits that have not yet found a standardized solution due to several trade-offs among different metrics such as energy consumption, speed, footprint, or fabrication complexity, to name a few. In particular, a photonic memory exhibiting ultra-high endurance performance (>106 cycles) has been elusive to date. Here, we report an ultra-high endurance silicon photonic volatile memory using vanadium dioxide (VO2) exhibiting a record cyclability of up to 107 cycles without degradation. Moreover, our memory features an ultra-compact footprint below 5 µm with the potential for nanosecond and picojoule programming performance. Our silicon photonic memory could find application in emerging photonic applications demanding a high number of memory updates, such as photonic neural networks with in situ training.

High‐Brightness and High‐Resolution Triboelectrification‐Induced Electroluminescence Skin for Photonic Imaging and Information Interaction

AbstractSelf‐powered visualized sensor with skin‐like functionality is highly anticipated for practical application in health monitoring, human‐machine interaction, and robotics. However, the existing methods are disadvantaged by their poor performance in sensitivity and spatial fidelity due to the low pixel density, brightness, or conformability. Herein, a novel self‐powered skin‐inspired visualized sensor (SP‐SIVS) is developed by means of triboelectrification‐induced electroluminescence (TIEL) technique. By integrating surface and bulk charge generation with a high‐voltage corona charging treatment, a significant improvement is achieved in the brightness (by 10‐fold) and spatial resolution (100 µm) of the SP‐SIVS. Meanwhile, Young's modulus (94 kPa) is maintained at a level comparable to human skin, with tensile strength and elongation exceeding 1000 kPa and 1000%, respectively. Furthermore, SP‐SIVS is verified as applicable to serve such purposes as wearable motion detection, fingerprint morphology imaging, and information interaction. This work contributes an innovative framework to the development of SP‐SIVS with high‐brightness, high‐resolution, and sustainability, laying a foundation for its popularization as a novel interactive medium required for advanced photonic applications.

BAs/BlueP van der Waals heterostructures for photovoltaic and thermoelectric applications

The advancement of novel energy materials, encompassing photovoltaic and thermoelectric materials, assumes paramount significance in ameliorating the energy crisis and proactively combating climate change. The BAs/BlueP van der Waals heterostructure (vdWH), characterized by its outstanding optical absorption properties, high power conversion efficiency (PCE), and excellent thermoelectric performance, offers novel insights into the advancement of materials for photonic and thermoelectric applications. We have engineered a vdWH by combining BAs and BlueP, and conducted a comprehensive investigation of its electronic, optical, and thermoelectric properties. The BAs/BlueP vdWH demonstrates excellent thermodynamic and kinetic stability with type I band alignment, facilitating rapid interlayer electron-hole recombination. The remarkable optical absorption capability within the visible and ultraviolet (UV) spectral regions, coupled with an outstanding power conversion efficiency reaching up to 22.35 % under strain, firmly establishes the potential for utilization in photovoltaic conversion applications. At 1000 K, the significant ZT value (1.25) and high thermoelectric conversion efficiency (19.45 %) provide the theoretical foundation for its application in the field of thermoelectrics.

Mn2+ doped Zn2SiO4 phosphors: A threefold-mode sensing approach for optical thermometry in the visible region at 525 nm

Optical functional materials such as nanostructured silicates have been studied for photonics applications involving energy conversion. In this scenario, we studied Zn2SiO4:Mn2+ nanostructured powders prepared by combustion synthesis for optical thermometry based on photon downshifting. The structural analysis showed that Zn2SiO4 particles were found embedded in clustered silica nanoparticles. The photoluminescence analysis showed that the samples exhibit intense green emission (centered around 525 nm), corresponding to the electronic transition 4T1 → 6A1 of Mn2+, when exposed to a low power ultraviolet lamp (centered around 255 nm). The temperature sensing performance of this material was evaluated using three different methodologies, i.e. the luminescence decay time constant, the spectral full width at half maximum, and the luminescence peak intensity from the 4T1 → 6A1 radiative transition. The thermometric analysis based on luminescence peak intensity provided a maximum relative sensitivity of ∼4.9x10−3 K−1 at 498 K, while the decay lifetime and the spectral width at half maximum provided maximum relative temperature sensitivities of ∼2.9x10−3 K−1 at 523 K and ∼1.7x10−3 K−1 at 298 K, respectively.

Perylene-3,4,9,10-tetracarboxylic dianhydride dye intercalated liquid crystal molecules: Synthesis, spectroscopic characterizations and photoluminescence dynamics

The present research explores the interaction between perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)-dye (PD) and 3b {(E)-1-[3-fluoro-4-(pentyloxy)phenyl]-2-(4-methylphenyl)diazene} liquid crystal (LC) mesophase, 3c{(E)-1-[3-fluoro-4-(hexyloxy)phenyl]-2-(4-methylphenyl)diazene} nematic liquid crystal (NLC) molecule. Spectroscopic characterizations of 3b@PD LC mesophase and 3c@PD NLC molecule were carried out using scanning electron microscopy (SEM), polarizing optical microscope (POM), Raman, Fourier transform infrared spectroscopy (FT-IR), and UV–visible analytical methods. The UV–visible studies revealed a red shift in absorption bands (348.0 nm to 374 nm) with a decrease in optical band gap from 2.43 eV to 2.25 eV. Room temperature photoluminescence (RTPL) spectra of 3b@PD LC mesophase exhibited blue light emission characteristics centred at 453.1 nm and 3c @PD NLC molecule showed broad emission peaks located at 400.7 nm and 324.8 nm. Steady-state photoluminescence (SSPL) spectra showcased indigo-purple emission bands corresponding to the wavelengths 303–353 nm, 420.5 nm, 418 nm, 418.3 nm, and 347.0 nm, however, for the 3c@PD NLC molecule, emission intensity peaks appeared at 429.6 nm, 418.0 nm and 329.0 nm. The stoke’s shift for 3b@PD LC mesophase varied between 0.01 eV to 0.613 eV while for 3c@PD NLC molecule it was found in between 0.317 eV to 0.453 eV. POM analysis unveiled distinct fan-like textures with varied colour interfaces. Time-resolved photoluminescence (TRPL) decay studies unveiled average lifetime of 3b@PD LC mesophase was 1.80 ns, 0.98 ns, 0.308 ns and for 3c@PD NLC molecule, the average lifetime was found to be 0.98 ns, 0.82 ns, and 0.306 ns at various excitation wavelengths. However, phosphorescence decay studies showed faster decay characteristics for 3c@PD NLC molecule (1.40 ns to 4.00 ns) compared with 3b@PD LC mesophase (1.65 to 5.42 ns) when excited at various wavelengths. The interaction between LC molecules and PTCDA demonstrated a significant enhancement in RTPL, TRPL, and SSPL properties, suggesting promising applications in photonics and optoelectronics.

Power dependent tunable optical nonlinearity in Iron oxide/Borophene core-shell nanoparticles under ultrashort laser excitation

Two-dimensional (2D) nanomaterials find immense applications in ultrafast photonics and optical switching systems due to their fascinating nonlinear optical (NLO) characteristics. This work presents a systematic investigation of laser power-dependent nonlinear optical characteristics of borophene nanosheets in a core-shell nanostructure. For this purpose, we have synthesized Borophene encapsulated Iron oxide (Fe3O4) core-shell nanoparticles (Fe3O4/Borophene CSNPs). The CSNPs were synthesized by mixing and annealing sodium borohydride (NaBH4) as a boron precursor with iron oxide nanoparticles (Fe3O4 NPs) in a controlled environment using chemical vapor deposition technique (CVD) followed by characterization using XRD, FTIR Spectroscopy, UV–vis absorption spectroscopy, TEM, SEM, and EDX techniques. Magnetic properties were analyzed by a vibrating sample magnetometer (VSM) which shows that the saturation magnetization of Fe3O4 NPs increases after being encapsulated in borophene nanosheets. The role of borophene in modifying the NLO characteristics of Fe3O4/Borophene CSNPs was studied using a power-dependent Z-scan technique utilizing ultrashort (femtosecond) laser pulses at a wavelength of 800 nm in both open and close aperture configuration. It was found that borophene-coated Fe3O4 NPs reveal tunable NLO properties that resemble the NLO characteristics of borophene nanosheets with enhanced features. This provides insights into an interaction between materials in NLO phenomena and illustrates the distinctive performance of the core-shell nanostructure. The tunable NLO properties of Fe3O4/Borophene CSNPs offer an innovative approach for developing optoelectronics and ultrafast nonlinear photonic devices.

Banana DNA derivatives as homeotropic alignment layers in optical devices.

In this study, deoxyribonucleic acid (DNA) from bananas was extracted and functionalized and used for the first time as a homeotropic alignment layer for liquid crystals (LCs). Our research was aimed at extracting and investigating DNA from bananas via the synthesis and study of DNA complexes with various surfactants to examine the usefulness of such a complex as an alignment layer in electro-optical transducers. We proposed a simple and eco-friendly synthesis of the DNA complexes isolated from bananas with surfactants, so we transformed the DNA isolated from bananas into a functionalized alignment layer. A biopolymer alignment layer like deoxyribonucleic acid (DNA) from a banana complexed with a cationic surfactant is an excellent alternative to a commonly used but toxic polyimide alignment layer. DNA-based materials are promising for photonic applications and biosensors because of their excellent optical and physical properties, biodegradability, and low production cost. The novelty of the research lies in the potential use of these materials as biodegradable biopolymer alignment layers for optical devices instead of conventional polymers, which are usually harmful for the environment.

Two-dimensional-lattice-confined single-molecule-like aggregates.

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes1,2, lasers3-5 andquantum technologies6,7, among others8-10. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. This two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

Two-Coordinate Gold(I) Complex with Rotational Freedom: A Platform Integrating Thermally Activated Delayed Fluorescence, Polymorphism, and Linearly Polarized Luminescence.

Two-coordinate coinage metal complexes have been exploited for various applications. Herein, a new donor-metal-acceptor (D-M-A) complex PZI-Au-TOT, using bulky pyrazine-fused N-heterocyclic carbene (PZI) and trioxytriphenylamine (TOT) ligands, was synthesized. PZI-Au-TOT displays decent thermally activated delayed fluorescence (TADF) with a quantum yield of 93% in doped film. The crystals of PZI-Au-TOT show simultaneous TADF, polymorphism, and linearly polarized luminescence (LPL). The polymorph-dependent emission properties with widely varied peaks from 560 to 655 nm are attributed to different packing modes in terms of isolated monomers, discrete π-π stacked dimers or dimer PLUS. Two well-defined microcrystals of PZI-Au-TOT exhibit linearly polarized thermally activated delayed fluorescence with a degree of polarization up to 0.64. This work demonstrates that the molecular rotational flexibility of D-M-A type complexes endows an integration of multiple functions into one complex through manipulation of supramolecular aggregation. This type of complexes is expected to serve as a versatile platform for the fabrication of crystal materialsfor advanced photonic applications.

Photonic defect modes in cholesteric liquid crystal resonators with embedded isotropic layers

Photonic defect modes are explored as a viable alternative to standard photonic band edge modes in photonic crystal applications, especially due to their typically high Q-factors and local density of states. For example, they can be used in nonlinearity enhancement, lasing, and cavity quantum electrodynamics. However, they are strongly dependent on any structural change and need to be well-controlled to ensure the desired resonance frequency. Here, we present a study of the photonic defect modes that appear in a structure where a layer of isotropic material is embedded between two layers of cholesteric liquid crystal (CLC), using full electrodynamics numerical simulations. We present typical transmission spectra and electric field profiles of selected defect modes and then analyze the influence of geometrical and material parameters on the eigenfrequencies and Q-factors of the modes within and around the photonic bandgap, including refractive indices and thicknesses of isotropic and liquid crystal layers, and different anchoring orientations at the boundaries of the isotropic defect layer. Additionally, a connection of such defect modes to previously extensively analyzed twist defect modes is given. Eigenmodes in asymmetric resonators are also presented, where CLC layers surrounding the intermediate isotropic layer are not equally thick, enabling biasing of specific directional light emission. More generally, this work aims to contribute to the understanding and design capability in topological soft matter photonics where defect mode lasing could be realized in CLC geometries with different singular and solitonic topological defect structures.

Perovskite Nanocrystals Initiate One‐Step Oxygen Tolerant PET‐RAFT Polymerization of Highly Loaded, Efficient Plastic Nanocomposites

AbstractLead halide perovskite nanocrystals (LHP‐NCs) incorporated within polymer matrices have emerged as promising materials for various photonic applications. However, challenges persist in achieving high‐quality nanocomposites due to low monomer conversion yields, restricted LHP‐NCs loadings, and difficulty in maintaining NCs integrity post‐polymerization. A novel protocol for synthesizing LHP‐NCs/poly(methyl methacrylate) nanocomposites in a single step via the NC‐initiated photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) method is presented. Polymerization initiation mediated by NCs surfaces under blue light enables the fabrication of homogeneous nanocomposites with NCs loadings up to 7% w/w and ≈90% monomer conversion even in the presence of oxygen. This process preserves the optical quality of the NCs and passivates NCs surface defects, resulting in nanocomposites exhibiting near unity luminescence efficiencies. The potential of this approach for producing highly loaded nanocomposites for radiation detection is validated by radioluminescence measurements showing light yield values of 6000 ph MeV−1 and fast scintillation dynamics with effective lifetime of 490 ps, showing promise for time‐of‐flight radiometry.

Phase‐Transition Photonic Brick for Reconfigurable Topological Pathways

AbstractTopological photonic insulators serve as highways for light propagation, enabling photons to be transported with topological protection and enriching the understanding of light‐matter interactions. However, the prohibitive fabrication and non‐reconfigurable functionality of current topological photonics seriously hinder its practical applications. Here, a revolutionary concept of phase‐transition photonic brick is theoretically proposed and experimentally demonstrated, which can be regarded as an ideal building block to develop reconfigurable highways for light propagations. The proposed modular photonic brick not only integrates the inherent benefits of both passive and active topological photonics, but also offers previously unattainable superiority, including flexible scalability, deformability, detachability, and recyclability. Leveraging these benefits, this work provides a groundbreaking topological platform that balances the reconfigurability, multifunctionality, low electrical energy consumption, and low device fabrication cost. By unlocking the potential of recyclable photonic bricks, the work represents a significant step toward realizing the extensive and sustainable practical applications of topological photonics in information processing, computing, communications, and beyond.

Purcell Enhancement and Spin Spectroscopy of Silicon Vacancy Centers in Silicon Carbide Using an Ultrasmall Mode-Volume Plasmonic Cavity.

Silicon vacancy (VSi) centers in 4H-silicon carbide have emerged as a strong candidate for quantum networking applications due to their robust electronic and optical properties, including a long spin coherence lifetime and bright, stable emission. Here, we report the integration of VSi centers with a plasmonic nanocavity to Purcell enhance the emission, which is critical for scalable quantum networking. Employing a simple fabrication process, we demonstrate plasmonic cavities that support a nanoscale mode volume and exhibit an increase in the spontaneous emission rate with a measured Purcell factor of up to 48. In addition to investigating the optical resonance modes, we demonstrate an improvement in the optical stability of the spin-preserving resonant optical transitions relative to the radiation-limited value. The results highlight the potential of nanophotonic structures for advancing quantum networking technologies and emphasize the importance of optimizing emitter-cavity interactions for efficient quantum photonic applications.

Boundary-localized many-body bound states in the continuum

Bound states in the continuum (BICs), referring to spatially localized bound states with energies falling within the range of extended modes, have been extensively investigated in single-particle systems, leading to diverse applications in photonics, acoustics, and other classical-wave systems. Recently, there has been theoretical interest in exploring many-body BICs in interacting quantum systems, which necessitate the careful design of impurity potentials or spatial profiles of interaction. Here, we propose a type of many-body BICs localized at boundaries, which can be purely induced by the uniform onsite interaction without requiring any specific design of impurity potential or nonlocal interaction. We numerically show that three or more interacting bosons can concentrate on the boundary of a homogeneous one-dimensional lattice, which is absent at single- and two-particle counterparts. Moreover, the eigenenergy of multi-boson bound states can embed within the continuous energy spectra of extended scattering states, thereby giving rise to interaction-induced boundary many-body BICs. Furthermore, by mapping Fock states of three and four bosons to nonlinear circuit networks, we experimentally simulate boundary many-body BICs. Our findings enrich the comprehension of correlated BICs beyond the single-particle level, and have the potential to inspire future investigations on exploring many-body BICs.

Silicon-28-Tetrafluoride as an Educt of Isotope-Engineered Silicon Compounds and Bulk Materials for Quantum Systems.

This review provides a summary of the existing literature on a crucial raw material for the production of isotopically pure semiconductors, which are essential for the development of second-generation quantum systems. Silicon-28-tetrafluoride (28SiF4) is used as an educt for several isotope-engineered chemicals, such as silane-28 (28SiH4) and silicon-28-trichloride (28SiHCl3), which are needed in the pursuit of various quantum technologies. We are exploring the entire chain from the synthesis of 28SiF4 to quantum applications. This includes the chemical properties of SiF4, isotopic enrichment, conversion to silanes, conversion to bulk 28Si and thin films, the physical properties of 28Si (spin neutrality, thermal conductivity, optical properties), and the applications in quantum computing, photonics, and quantum sensing techniques.

A [2.2]Isoindolinophanyl-Based Carbene (iPC) Ligand: Synthesis, Electronic and Photophysical Properties, and Application in Photocatalysis.

Cyclic amino(alkyl) and cyclic amino(aryl) carbenes (cAACs/cAArCs) have been established as very useful ligands for catalytic and photonic applications of transition metal complexes. Herein, we describe the synthesis of a structurally related sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) that bears a [2.2]paracyclophane moiety. The latter leads to more delocalized frontier orbitals and intense green fluorescence of (HiPC)OTf (2) from an intra-ligand charge transfer (1ILCT) state in the solid state. Base-promoted synthesis of the free carbene led to an unusual ring expansion and subsequent dimerization reaction, but the beneficial ligand properties can be exploited by trapping in situ at a metal center. The iPC ligand is a very potent π-chromophore, which participates in low energy metal-to-ligand (ML)CT transitions in [RhCl(CO)2(iPC)] (4) and IL-"through-space"-CT transitions in [Au(iPC)2]OTf (5). The steric demand of the iPC leads to high stability of 5 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 μs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 5, which outperformed other established photocatalysts in comparison.