skip to main content


Title: Two-photon excited deep-red and near-infrared emissive organic co-crystals
Abstract

Two-photon excited near-infrared fluorescence materials have garnered considerable attention because of their superior optical penetration, higher spatial resolution, and lower optical scattering compared with other optical materials. Herein, a convenient and efficient supramolecular approach is used to synthesize a two-photon excited near-infrared emissive co-crystalline material. A naphthalenediimide-based triangular macrocycle and coronene form selectively two co-crystals. The triangle-shaped co-crystal emits deep-red fluorescence, while the quadrangle-shaped co-crystal displays deep-red and near-infrared emission centered on 668 nm, which represents a 162 nm red-shift compared with its precursors. Benefiting from intermolecular charge transfer interactions, the two co-crystals possess higher calculated two-photon absorption cross-sections than those of their individual constituents. Their two-photon absorption bands reach into the NIR-II region of the electromagnetic spectrum. The quadrangle-shaped co-crystal constitutes a unique material that exhibits two-photon absorption and near-infrared emission simultaneously. This co-crystallization strategy holds considerable promise for the future design and synthesis of more advanced optical materials.

 
more » « less
Award ID(s):
1836392
NSF-PAR ID:
10191945
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
11
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2- b ]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exhibit one-photon absorption in the 500–600 nm range with the peak molar extinction coefficients reaching 150 000, and emission in the 520–670 nm range with the fluorescence quantum yields reaching 0.90. Within the family of these ultrastable dyes even small structural changes lead to significant variations of the photophysical properties, in some cases attributed to reversal of energy ordering of alternate-parity excited electronic states. Effective preservation of ground-state inversion symmetry was evidenced by very weak two-photon absorption (2PA) at excitation wavelengths corresponding to the lowest-energy, strongly one-photon allowed purely electronic transition. π-Expanded derivatives and those possessing electron-donating groups showed the most red-shifted absorption- and emission spectra, while displaying remarkably high peak 2PA cross-section ( σ 2PA ) values reaching ∼2400 GM at around 760 nm, corresponding to a two-photon allowed higher-energy excited state. At the same time, derivatives lacking π-expansion were found to have a relatively weak 2PA peak centered at ca. 800–900 nm with the maximum σ 2PA ∼50–250 GM. Our findings are augmented by theoretical calculations performed using TD-DFT method, which reproduce the main experimental trends, including the 2PA, in a nearly quantitative manner. Electrochemical studies revealed that the HOMO of the new dyes is located at ca . −5.35 eV making them relatively electron rich in spite of the presence of two B − –N + dative bonds. These dyes undergo a fully reversible first oxidation, located on the diphenylpyrrolo[3,2- b ]pyrrole core, directly to the di(radical cation) stage. 
    more » « less
  2. Abstract High-precision placement of rare-earth ions in scalable silicon-based nanostructured materials exhibiting high photoluminescence (PL) emission, photostable and polarized emission, and near-radiative-limited excited state lifetimes can serve as critical building blocks toward the practical implementation of devices in the emerging fields of nanophotonics and quantum photonics. Introduced herein are optical nanostructures composed of arrays of ultrathin silicon carbide (SiC) nanowires (NWs) that constitute scalable one-dimensional NW-based photonic crystal (NW-PC) structures. The latter are based on a novel, fab-friendly, nanofabrication process. The NW arrays are grown in a self-aligned manner through chemical vapor deposition. They exhibit a reduction in defect density as determined by low-temperature time-resolved PL measurements. Additionally, the NW-PC structures enable the positioning of erbium (Er 3+ ) ions with an accuracy of 10 nm, an improvement on the current state-of-the-art ion implantation processes, and allow strong coupling of Er 3+ ions in NW-PC. The NW-PC structure is pivotal in engineering the Er 3+ -induced 1540-nm emission, which is the telecommunication wavelength used in optical fibers. An approximately 60-fold increase in the room-temperature Er 3+ PL emission is observed in NW-PC compared to its thin-film analog in the linear pumping regime. Furthermore, 22 times increase in the Er 3+ PL intensity per number of exited Er ions in NW-PC was observed at saturation while using 20 times lower pumping power. The NW-PC structures demonstrate broadband and efficient excitation characteristics for Er 3+ , with an absorption cross-section (~2 × 10 −18 cm 2 ) two-order larger than typical benchmark values for direct absorption in rare-earth-doped quantum materials. Experimental and simulation results show that the Er 3+ PL is photostable at high pumping power and polarized in NW-PC and is modulated with NW-PC lattice periodicity. The observed characteristics from these technologically friendly nanophotonic structures provide a promising route to the development of scalable nanophotonics and formation of single-photon emitters in the telecom optical wavelength band. 
    more » « less
  3. Abstract

    The synthesis and characterization is reported of (C9NH20)2SnBr4, a novel organic metal halide hybrid with a zero‐dimensional (0D) structure, in which individual seesaw‐shaped tin (II) bromide anions (SnBr42−) are co‐crystallized with 1‐butyl‐1‐methylpyrrolidinium cations (C9NH20+). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep‐red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr42−species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.

     
    more » « less
  4. Abstract

    The synthesis and characterization is reported of (C9NH20)2SnBr4, a novel organic metal halide hybrid with a zero‐dimensional (0D) structure, in which individual seesaw‐shaped tin (II) bromide anions (SnBr42−) are co‐crystallized with 1‐butyl‐1‐methylpyrrolidinium cations (C9NH20+). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep‐red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr42−species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.

     
    more » « less
  5. A new family of fluorescent thiophene and thienothiophene-containing squaraine dyes is described with tunable wavelengths that cover the absorption/emission range of 600–800 nm. The deep-red and near-infrared fluorescent compounds were easily prepared by simple synthesis and purification methods. Spectral studies showed that each squaraine was rapidly encapsulated by a tetralactam macrocycle, with nanomolar affinity in water, to produce a threaded supramolecular complex with high chemical stability, increased fluorescence quantum yield, and decreased fluorescence quenching upon dye self-aggregation. Energy transfer within the supramolecular complex permitted multiplex emission. That is, two separate dyes with fluorescence emission bands that match the popular Cy5 and Cy7 channels, could be simultaneously excited with a beam of 375 nm light. A broad range of practical applications is envisioned in healthcare diagnostics, microscopy, molecular imaging, and fluorescence-guided surgery. 
    more » « less