Side-functionalized two-dimensional polymers synthesized via on-surface Schiff-base coupling

Xu, Lirong; Cao, Lili; Guo, Zongxia; Zha, Zeqi; Lei, Shengbin

doi:10.1039/c5cc02232k

Cited by 27 publications

(27 citation statements)

References 37 publications

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“…With suitable precursors, there is no inherent limitation, however, to extend the surface-assisted synthesis to more complex 2D polymers that feature functionalized pores2829. The functional groups facing the pores lay the foundation to further tune the electronic properties of porous graphene networks.…”

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confidence: 99%

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

et al. 2017

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The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

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confidence: 99%

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

et al. 2017

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“…The polymers in this study: poly(phenyl-azomethine-phenyl) P(PI-IPI) and poly(2,5-dihydroxybenzene-azomethine-phenyl-azomethine) P(PIOH-IPI) were synthesized via Schiff base condensation reaction [19][20][21]. The polymers P(PI-IPI) and P(PIOH-IPI) were formed via the mixing of terephthalaldehyde (Tph-CHO) with benzenediamine (DAB) and 2,5-Diaminohydroquinone dihydrochloride (DAH), respectively (scheme 1).…”

Section: Results and Discussion Synthesis And Characterization And Phymentioning

confidence: 99%

“…The polymers are synthesized as reported in the previous literature [18][19][20]. An equimolar of terephthalaldehyde (Tph-CHO) and aryl-diamines was mixed in acetonitrile solution at RT and stirred for 6 hr.…”

Section: Procedures Reaction/ Synthesis Of Polymersmentioning

confidence: 99%

Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Aljaafreh

Altarawneh

Alomari

et al. 2017

J. Pure App. Chem. Res.

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In this report, a synergetic computational and experimental studies were demonstrated on examples of poly-imine polymers; P(PI-IPI) and P(PIOH-IPI) to explore the role of hydroxyl substituent on their sensing and electronic properties. The polymer P(PIOH-IPI) bearing the OH-group on the ortho-position to the imine-bond, while the structure of the polymer P(PI-IPI) reveal the imine-bond only. The sensing property of the polymers was investigated via the UV-vis absorption in different solvents, acidic and basic solutions. Both polymers have shown significant sensing behavior in the acidic medium, while unpronounced behavior was noticed in the case of the polymer P(PI-IPI) in basic medium. Upon the incorporation of the OH-group, the polymer P(PIOH-IPI) has indistinguishable sensing behavior, a similar blue-shift in the acidic and basic medium, which can be attributed to the presence and the position of OH-group. The optical band gap of the polymers was determined experimentally and theoretically from the UV-vis absorption spectra and DFT calculations in the DMSO solvent. Other factors that affect the band gap values such as the structural conformation and length of conjugation were explored theoretically. In general, as the length of the optimized chain increased, the spectrum is red-shifted and the band gap decreased, which is attributed to the possible loss of chain planarity and conjugation beyond the monomer structure. Interestingly, the UV-vis spectra of the monomer-optimized structures were in a good match with the experimental UV-vis spectra. However, the band gap difference can be attributed to the method of band gap determination.Key word: Sensing, Functionalization, conformation, Length of conjugation, DFT, UV-vis INTRODUCTIONImine-linked polymers (ILPs) are organic conjugated polymers that gained significant importance due to their vital applications in the fields of catalysis, sensing, gas sorption, electronic and optoelectronic devices, sensors and other more applications [1][2][3][4][5][6][7]. The multifunctional properties of ILPs are related to their selective structural design which, exhibit an extended conjugated backbone accessible for functionalization and free nitrogen sites available for protonation and metal ion-coordination [3,8,9].As example, ILPs-based polymers such as C3v-POF and Th-POF were synthesized as Cu-and Ir-coordinated polymers and used as catalysts in the hydrogenation and cyclopropanation reactions, while other ILPs were used as Suzuki coupling catalysts [9][10][11].

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“…In particular,C OFs based on 2D p-conjugated structures are extremelyinteresting. [99,104,105] Various type of 2D COFs have been obtained by meanso f on-surface synthesis through different types of reactions, for example, polycondensation that involves boronic acid derivatives [106][107][108] or Schiff bases, [71,76,88] therebyr esulting in extended porousn etworks of high structural quality and large domain size. [58,[99][100][101][102] Moreover,f unctionalized 2D COFs hold the potential to serve as ac helating agent and therefore can be used in the preparationo fm olecularscale membranes with well-ordered recognition sites toward metal ions, which could find applications in sensing [103] or catalysis.…”

Section: D Covalent Organic Frameworkmentioning

confidence: 99%

Imine‐Based Architectures at Surfaces and Interfaces: From Self‐Assembly to Dynamic Covalent Chemistry in 2D

Janica

Patroniak

Samorı́

et al. 2018

Chemistry An Asian Journal

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Within the last two decades, dynamic covalent chemistry (DCC) has emerged as an efficient and versatile strategy for the design and synthesis of complex molecular systems in solution. While early examples of supramolecularly assisted covalent synthesis at surfaces relied strongly on kinetically controlled reactions for post-assembly covalent modification, the DCC method takes advantage of the reversible nature of bond formation and allows the generation of the new covalently bonded structures under thermodynamic control. These structurally complex architectures obtained by means of DCC protocols offer a wealth of solutions and opportunities in the generation of new complex materials that possess sophisticated properties. In this focus review we examine the formation of covalently bonded imine-based discrete nanostructures as well as one-dimensional (1D) polymers and two-dimensional (2D) covalent organic frameworks (COFs) physisorbed on solid substrates under various experimental conditions, for example, under ultra-high vacuum (UHV) or at the solid-liquid interface. Scanning tunneling microscopy (STM) was used to gain insight, with a sub-nanometer resolution, into the structure and properties of those complex nanopatterns.

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Side-functionalized two-dimensional polymers synthesized via on-surface Schiff-base coupling

Cited by 27 publications

References 37 publications

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

Investigation of the Electronic and pH-Sensing properties of Hydroxyl-Functionalized Imine-Linked Polymers via the UV-vis Absorption Spectra and the Density Functional Theory (DFT) Calculations

Imine‐Based Architectures at Surfaces and Interfaces: From Self‐Assembly to Dynamic Covalent Chemistry in 2D

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