skip to main content


Title: Dynamic B/N Lewis Pairs: Insights into the Structural Variations and Photochromism via Light‐Induced Fluorescence to Phosphorescence Switching
Abstract

Ultralong afterglow emissions due to room‐temperature phosphorescence (RTP) are of paramount importance in the advancement of smart sensors, bioimaging and light‐emitting devices. We herein present an efficient approach to achieve rarely accessible phosphorescence of heavy atom‐free organoboranes via photochemical switching of sterically tunable fluorescent Lewis pairs (LPs). LPs are widely applied in and well‐known for their outstanding performance in catalysis and supramolecular soft materials but have not thus far been exploited to develop photo‐responsive RTP materials. The intramolecular LPM1BNMnot only shows a dynamic response to thermal treatment due to reversible N→B coordination but crystals ofM1BNMalso undergo rapid photochromic switching. As a result, unusual emission switching from short‐lived fluorescence to long‐lived phosphorescence (radM1BNM,τRTP=232 ms) is observed. The reported discoveries in the field of Lewis pairs chemistry offer important insights into their structural dynamics, while also pointing to new opportunities for photoactive materials with implications for fast responsive detectors.

 
more » « less
NSF-PAR ID:
10385112
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie
Volume:
134
Issue:
51
ISSN:
0044-8249
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Ultralong afterglow emissions due to room‐temperature phosphorescence (RTP) are of paramount importance in the advancement of smart sensors, bioimaging and light‐emitting devices. We herein present an efficient approach to achieve rarely accessible phosphorescence of heavy atom‐free organoboranes via photochemical switching of sterically tunable fluorescent Lewis pairs (LPs). LPs are widely applied in and well‐known for their outstanding performance in catalysis and supramolecular soft materials but have not thus far been exploited to develop photo‐responsive RTP materials. The intramolecular LPM1BNMnot only shows a dynamic response to thermal treatment due to reversible N→B coordination but crystals ofM1BNMalso undergo rapid photochromic switching. As a result, unusual emission switching from short‐lived fluorescence to long‐lived phosphorescence (radM1BNM,τRTP=232 ms) is observed. The reported discoveries in the field of Lewis pairs chemistry offer important insights into their structural dynamics, while also pointing to new opportunities for photoactive materials with implications for fast responsive detectors.

     
    more » « less
  2. Abstract

    Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B−N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2and acetylene, and soft polymer networks that serve as recyclable, self‐healing, and responsive thermosets, gels and elastomeric materials.

     
    more » « less
  3. Abstract

    Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B−N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2and acetylene, and soft polymer networks that serve as recyclable, self‐healing, and responsive thermosets, gels and elastomeric materials.

     
    more » « less
  4. null (Ed.)
    Sulfur oxidation state is used to tune organic room temperature phosphorescence (RTP) of symmetric sulfur-bridged carbazole dimers. The sulfide-bridged compound exhibits a factor of 3 enhancement of the phosphorescence efficiency, compared to the sulfoxide and sulfone-bridged analogs, despite sulfone bridges being commonly used in RTP materials. In order to investigate the origin of this enhancement, temperature dependent spectroscopy measurements and theoretical calculations are used. The RTP lifetimes are similar due to similar crystal packing modes. Computational studies reveal that the lone pairs on the sulfur atom have a profound impact on enhancing intersystem crossing rate through orbital mixing and screening, which we hypothesize is the dominant factor responsible for increasing the phosphorescence efficiency. The ability to tune the electronic state without altering crystal packing modes allows the isolation of these effects. This work provides a new perspective on the design principles of organic phosphorescent materials, going beyond the rules established for conjugated ketone/sulfone-based organic molecules. 
    more » « less
  5. By mimicking biomimetic synaptic processes, the success of artificial intelligence (AI) has been astounding with various applications such as driving automation, big data analysis, and natural-language processing.[1-4] Due to a large quantity of data transmission between the separated memory unit and the logic unit, the classical computing system with von Neumann architecture consumes excessive energy and has a significant processing delay.[5] Furthermore, the speed difference between the two units also causes extra delay, which is referred to as the memory wall.[6, 7] To keep pace with the rapid growth of AI applications, enhanced hardware systems that particularly feature an energy-efficient and high-speed hardware system need to be secured. The novel neuromorphic computing system, an in-memory architecture with low power consumption, has been suggested as an alternative to the conventional system. Memristors with analog-type resistive switching behavior are a promising candidate for implementing the neuromorphic computing system since the devices can modulate the conductance with cycles that act as synaptic weights to process input signals and store information.[8, 9]

    The memristor has sparked tremendous interest due to its simple two-terminal structure, including top electrode (TE), bottom electrode (BE), and an intermediate resistive switching (RS) layer. Many oxide materials, including HfO2, Ta2O5, and IGZO, have extensively been studied as an RS layer of memristors. Silicon dioxide (SiO2) features 3D structural conformity with the conventional CMOS technology and high wafer-scale homogeneity, which has benefited modern microelectronic devices as dielectric and/or passivation layers. Therefore, the use of SiO2as a memristor RS layer for neuromorphic computing is expected to be compatible with current Si technology with minimal processing and material-related complexities.

    In this work, we proposed SiO2-based memristor and investigated switching behaviors metallized with different reduction potentials by applying pure Cu and Ag, and their alloys with varied ratios. Heavily doped p-type silicon was chosen as BE in order to exclude any effects of the BE ions on the memristor performance. We previously reported that the selection of TE is crucial for achieving a high memory window and stable switching performance. According to the study which compares the roles of Cu (switching stabilizer) and Ag (large switching window performer) TEs for oxide memristors, we have selected the TE materials and their alloys to engineer the SiO2-based memristor characteristics. The Ag TE leads to a larger memory window of the SiO2memristor, but the device shows relatively large variation and less reliability. On the other hand, the Cu TE device presents uniform gradual switching behavior which is in line with our previous report that Cu can be served as a stabilizer, but with small on/off ratio.[9] These distinct performances with Cu and Ag metallization leads us to utilize a Cu/Ag alloy as the TE. Various compositions of Cu/Ag were examined for the optimization of the memristor TEs. With a Cu/Ag alloying TE with optimized ratio, our SiO2based memristor demonstrates uniform switching behavior and memory window for analog switching applications. Also, it shows ideal potentiation and depression synaptic behavior under the positive/negative spikes (pulse train).

    In conclusion, the SiO2memristors with different metallization were established. To tune the property of RS layer, the sputtering conditions of RS were varied. To investigate the influence of TE selections on switching performance of memristor, we integrated Cu, Ag and Cu/Ag alloy as TEs and compared the switch characteristics. Our encouraging results clearly demonstrate that SiO2with Cu/Ag is a promising memristor device with synaptic switching behavior in neuromorphic computing applications.

    Acknowledgement

    This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

    References

    [1] Younget al.,IEEE Computational Intelligence Magazine,vol. 13, no. 3, pp. 55-75, 2018.

    [2] Hadsellet al.,Journal of Field Robotics,vol. 26, no. 2, pp. 120-144, 2009.

    [3] Najafabadiet al.,Journal of Big Data,vol. 2, no. 1, p. 1, 2015.

    [4] Zhaoet al.,Applied Physics Reviews,vol. 7, no. 1, 2020.

    [5] Zidanet al.,Nature Electronics,vol. 1, no. 1, pp. 22-29, 2018.

    [6] Wulfet al.,SIGARCH Comput. Archit. News,vol. 23, no. 1, pp. 20–24, 1995.

    [7] Wilkes,SIGARCH Comput. Archit. News,vol. 23, no. 4, pp. 4–6, 1995.

    [8] Ielminiet al.,Nature Electronics,vol. 1, no. 6, pp. 333-343, 2018.

    [9] Changet al.,Nano Letters,vol. 10, no. 4, pp. 1297-1301, 2010.

    [10] Qinet al., Physica Status Solidi (RRL) - Rapid Research Letters, pssr.202200075R1, In press, 2022.

     
    more » « less