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1.
J Am Chem Soc ; 142(35): 15038-15048, 2020 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-32786794

RESUMO

The creation of 1D π-conjugated nanofibers with precise control and optimized optoelectronic properties is of widespread interest for applications as nanowires. "Living" crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D fiber-like micelles from a range of crystallizable polymeric amphiphiles. However, in the case of polythiophenes, one of the most important classes of conjugated polymer, only limited success has been achieved to date using block copolymers as precursors. Herein, we describe studies of the living CDSA of phosphonium-terminated amphiphilic poly(3-hexylthiophene)s to prepare colloidally stable nanofibers. In depth studies of the relationship between the degree of polymerization and the self-assembly behavior permitted the unveiling of the energy landscape of the living CDSA process. On the basis of the kinetic and thermodynamic insight provided, we have been able to achieve an unprecedented level of control over the length of low dispersity fiber-like micelles from 40 nm to 2.8 µm.

2.
Dalton Trans ; 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32691789

RESUMO

The synthesis of heteroleptic complexes with calcium- and magnesium-tin bonds is described. The dimeric ß-diketiminato calcium hydride complex, [(BDI)Ca(µ-H)]2 (ICa) reacts with Ph3Sn-SnPh3 to provide the previously reported µ2-H bridged calcium stannanide dimer, [(BDI)2Ca2(SnPh3)(µ-H)] (3). Computational assessment of this reaction supports a mechanism involving a hypervalent stannate intermediate formed by nucleophilic attack of hydride on the distannane. Monomeric calcium stannanides, [(BDI)Ca(SnPh3)·OPPh3] (8·OPPh3) and [(BDI)Ca(SnPh3)·TMTHF] (8·TMTHF, TMTHF = 2,2,5,5-tetramethyltetrahydrofuran) were obtained from ICa and Ph3Sn-SnPh3, after addition OPPh3 or TMTHF. Both complexes were also synthesised by deprotonation of Ph3SnH by ICa in the presence of the Lewis base. The calcium and magnesium THF adducts, [(BDI)Ca(SnPh3)·THF2] (8·THF2) and [(BDI)Mg(SnPh3)·THF] (9·THF), were similarly prepared from [(BDI)Ca(µ-H)·(THF)]2 (ICa·THF2) or [(BDI)Mg(µ-H)]2 (IMg) and Ph3SnH. An excess of THF or TMTHF was essential in order to obtain 8·TMTHF, 8·THF2 and 9·THF in high yields whilst avoiding redistribution of the phenyl-tin ligand. The resulting Ae-Sn complexes were used as a source of [Ph3Sn]- in salt metathesis, to provide the known tristannane Ph3Sn-Sn(t-Bu)2-SnPh3 (11). Nucleophilic addition or insertion with N,N'-di-iso-propylcarbodiimide provided the stannyl-amidinate complexes, [(BDI)Mg{(iPrN)2CSnPh3}] (12) and [(BDI)Ca{(iPrN)2CSnPh3}·L] (13·TMTHF, 13·THF, L = TMTHF, THF). The reactions and products were monitored and characterised by multinuclear NMR spectroscopy, whilst for compounds 8, 9, 12, and 13·THF, the X-ray crystal structures are presented and discussed.

3.
J Am Chem Soc ; 142(31): 13469-13480, 2020 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-32594739

RESUMO

The creation of organic heterojunctions from conjugated polymers on the nanoscale has attracted recent attention as a consequence of their considerable potential in optoelectronic devices. Herein, we report proof-of-concept results on a versatile synthetic strategy to access various linearly segmented nanowire heterojunctions with controlled dimensions using the seeded growth "living crystallization-driven self-assembly" method followed by a secondary crystallization step. Specifically, we describe the creation of coaxial and also segmented coaxial B-A-B and A-B-A nanowires with a solvophilic poly(ethylene glycol) (PEG) corona, an inner crystalline core that consists of poly(di-n-hexylfluorene) (PDHF), which functions as a donor, and an outer crystalline core of poly(3-(2'-ethylhexyl)thiophene) (P3EHT), which acts as an acceptor. The latter is present either along the entire nanowire or solely in the central or terminal segments. These assemblies were created by seeded growth of two types of π-conjugated polymeric building blocks, the triblock copolymer PDHF-b-P3EHT-b-PEG and the diblock copolymer PDHF-b-PEG, by using fiber-like seeds derived from either material. The nanowires with both solid-state donor and acceptor blocks exhibit Förster resonance energy transfer (FRET) from the PDHF inner core to the P3EHT outer core which was characterized by fluorescence spectroscopy and laser confocal scanning fluorescence microscopy (LCSM). The FRET in the solid-state coaxial heterojunctions with an inner PDHF core and an outer P3EHT core was enhanced relative to the directly analogous system in which the P3EHT block was solvated.

4.
Artigo em Inglês | MEDLINE | ID: mdl-32243037

RESUMO

Self-assembly of d8 metal polypyridine systems is a well-established approach for the creation of 1D organometallic assemblies but there are still challenges for the large-scale construction of nanostructured patterns from these building blocks. We describe herein the use of high-throughput nanoimprint lithography (NIL) to direct the self-assembly of the bimetallic complexes [4'-ferrocenyl-(2,2':6',2''-terpyridine)M(OAc)]+ (OAc)- (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self-organization and evidenced by morphological characterization. More importantly, when top-down NIL is coupled with the bottom-up self-assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit-patterned media.

5.
Chem Commun (Camb) ; 2020 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-32211641

RESUMO

This work presents a simple approach to access uniform fiber-like micelles by single-step crystalization-driven co-self-assembly of a polyferrocenyldimethylsilane (PFS) block copolymer with a trace of a PFS homopolymer. The length of micelles in the µm range could be controlled by changing the amount of homopolymer in the mixture.

6.
Angew Chem Int Ed Engl ; 59(21): 8232-8239, 2020 05 18.
Artigo em Inglês | MEDLINE | ID: mdl-32022396

RESUMO

Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV5 -b-P2VP44 ), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV5 -b-P2VP44 with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV5 -b-PNIPAM49 and OPV5 -b-P2VP44 to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities.

7.
Chemistry ; 26(13): 2954-2966, 2020 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-31899846

RESUMO

The dehydrocoupling of silanes and alcohols mediated by heavier alkaline-earth catalysts, [Ae{N(SiMe3 )2 }2 ⋅(THF)2 ] (I-III) and [Ae{CH(SiMe3 )2 }2 ⋅(THF)2 ], (IV-VI) (Ae=Ca, Sr, Ba) is described. Primary, secondary, and tertiary alcohols were coupled to phenylsilane or diphenylsilane, whereas tertiary silanes are less tolerant towards bulky substrates. Some control over reaction selectivity towards mono-, di-, or tri-substituted silylether products was achieved through alteration of reaction stoichiometry, conditions, and catalyst. The ferrocenyl silylether, FeCp(C5 H4 SiPh(OBn)2 ) (2), was prepared and fully characterized from the ferrocenylsilane, FeCp(C5 H4 SiPhH2 ) (1), and benzyl alcohol using barium catalysis. Stoichiometric experiments suggested a reaction manifold involving the formation of Ae-alkoxide and hydride species, and a series of dimeric Ae-alkoxides [(Ph3 CO)Ae(µ2 -OCPh3 )Ae(THF)] (3 a-c, Ae=Ca, Sr, Ba) were isolated and fully characterized. Mechanistic experiments suggested a complex reaction mechanism involving dimeric or polynuclear active species, whose kinetics are highly dependent on variables such as the identity and concentration of the precatalyst, silane, and alcohol. Turnover frequencies increase on descending Group 2 of the periodic table, with the barium precatalyst III displaying an apparent first-order dependence in both silane and alcohol, and an optimum catalyst loading of 3 mol % Ba, above which activity decreases. With precatalyst III in THF, ferrocene-containing poly- and oligosilylethers with ferrocene pendent to- (P1-P4) or as a constituent (P5, P6) of the main polymer chain were prepared from 1 or Fe(C5 H4 SiPhH2 )2 (4) with diols 1,4-(HOCH2 )2 -(C6 H4 ) and 1,4-(CH(CH3 )OH)2 -(C6 H4 ), respectively. The resultant materials were characterized by NMR spectroscopy, gel permeation chromatography (GPC) and DOSY NMR spectroscopy, with estimated molecular weights in excess of 20,000 Da for P1 and P4. The iron centers display reversible redox behavior and thermal analysis showed P1 and P5 to be promising precursors to magnetic ceramic materials.

8.
J Colloid Interface Sci ; 560: 50-58, 2020 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-31639564

RESUMO

HYPOTHESIS: Crystallization-driven self-assembly (CDSA) of block copolymers (BCPs) with a crystallizable core-forming oligo(p-phenylenevinylene) (OPV) segment can be a powerful strategy for the preparation of uniform fiber-like nanostructures containing a π-conjugated core with controlled dimension and composition. However, the self-assembly landscape can be complex, and our understanding of the nucleation and growth processes in the CDSA of BCPs with a crystalline π-conjugated segment is limited. EXPERIMENTS: We used fluorescence spectroscopy and 1H NMR to follow the self-assembly of oligo(p-phenylenevinylene)-b-poly(N-isopropyl acrylamide) (OPV5-b-PNIPAM49), a typical π-conjugated-coil BCP, as solution of the BCP in ethanol is cooled from 80 °C to 23 °C and allowed to age, µDSC to monitor the crystallization exotherm, and DLS and TEM to follow micelle growth. We see a striking difference in the experiments that monitor unimer in solution comparing to those that monitor micelle growth. We see nearly complete disappearance of unimer within 30 min upon cooling. In contrast, the micelles continue to grow, increasing in length by a factor of ten over the next several hours. We are able to exclude growth by end-to-end coupling. FINDINGS: We propose a self-assembly mechanism in which short semi-crystalline rod-like micelles form upon cooling, accompanied by small amorphous aggregates. Unimers that dissociate from these aggregates subsequently deposit on the growing ends of the core-crystalline micelles. We also find that the length of the PNIPAM block affects the elongation kinetics of OPV5-b-PNIPAM.

9.
Macromol Rapid Commun ; 41(4): e1900468, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31880037

RESUMO

Catalytic dehydropolymerization of halogen-functionalized phosphine-boranes (4-X-C6 H4 )PH2 ⋅BH3 (1a: X = Br, 1b: X = I) with [CpFe(CO)2 (OTf)] at 100 °C provides convenient access to halogen-functionalized polyphosphinoboranes [(4-X-C6 H4 )PH-BH2 ]n (2a: X = Br, 2b: X = I). These polymers are useful precursors for post-polymerization functionalization, which is demonstrated by Sonogashira coupling under mild conditions to yield the alkynyl-functionalized polyphosphinoborane [(4-PhCC-C6 H4 )PH-BH2 ]n (3).


Assuntos
Boranos/química , Halogênios/química , Fosfinas/química , Polímeros/química , Polímeros/síntese química , Alquinos/química , Catálise , Polimerização
10.
Science ; 366(6469): 1095-1098, 2019 11 29.
Artigo em Inglês | MEDLINE | ID: mdl-31780551

RESUMO

The creation of nanostructures with precise chemistries on material surfaces is of importance in a wide variety of areas such as lithography, superhydrophobicity, and cell adhesion. We describe a platform for surface functionalization that involves the fabrication of cylindrical micellar brushes on a silicon wafer through seeded growth of crystallizable block copolymers at the termini of immobilized, surface-confined crystallite seeds. The density, length, and coronal chemistry of the micellar brushes can be precisely tuned, and post-growth decoration with nanoparticles enables applications in catalysis and antibacterial surface modification. The micellar brushes can also be grown on ultrathin two-dimensional materials such as graphene oxide nanosheets and further assembled into a membrane for the separation of oil-in-water emulsions and gold nanoparticles.

11.
J Am Chem Soc ; 141(51): 20009-20015, 2019 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-31756293

RESUMO

We report well-defined Ti(III) metallocene complexes Cp*2TiMe (1Me) and Cp*2TiH (1H) (Cp* = η5-C5Me5) as the first isolable early transition metal precatalysts for the dehydropolymerization of amine-boranes RNH2·BH3. These earth-abundant metal catalysts combine high activity with broad substrate scope. In contrast to late transition metal catalysts, 1Me displays reactivity toward a variety of primary amine-boranes, including those containing reactive moieties such as olefinic groups. The ability to functionalize the side chain of the resultant polyaminoborane [RNH-BH2]n provides a promising method for controlling properties. Mechanistic investigation of the dehydrogenation of secondary amine-borane Me2NH·BH3 supports a bond-metathesis/ß-hydride elimination, redox-neutral mechanism with a Ti(III)-H resting state.

12.
Chem Commun (Camb) ; 55(86): 12964-12967, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31603152

RESUMO

Reaction of the dimeric calcium hydride, [(BDI)CaH]2 (1), with Ph3SnH ensues with elimination of H2 to provide [(BDI)Ca-µ2-H-(SnPh3)Ca(BDI)] (3) and [(BDI)Ca(SnPh3)]2 (4) alongside dismutation to Ph4Sn, H2 and Sn(0). DFT analysis indicates that stannyl anion formation occurs through deprotonation of Ph3SnH and with retention of dinuclear species throughout the reactions.

13.
J Am Chem Soc ; 141(48): 19088-19098, 2019 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-31657915

RESUMO

Fiber-like micelles based on biodegradable and biocompatible polymers exhibit considerable promise for applications in nanomedicine, but until recently no convenient methods were available to prepare samples with uniform and controllable dimensions and spatial control of functionality. "Living" crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D and 2D core-shell nanoparticles from a range of crystallizable polymeric amphiphiles. However, in the case of poly(l-lactide) (PLLA), arguably the most widely utilized biodegradable polymer as the crystallizable core-forming block, the controlled formation of uniform fiber-like structures over a substantial range of lengths by "living" CDSA has been a major challenge. Herein, we demonstrate that via simple modulation of the solvent conditions via the addition of trifluoroethanol (TFE), DMSO, DMF and acetone, uniform fiber-like nanoparticles from PLLA diblock copolymers with controlled lengths up to 1 µm can be prepared. The probable mechanism involves improved unimer solvation by a reduction of hydrogen bonding interactions among PLLA chains. We provide evidence that this minimizes undesirable unimer aggregation which otherwise favors self-nucleation that competes with epitaxial crystallization from seed termini. This approach has also allowed the formation of well-defined segmented block comicelles with PLLA cores via the sequential seeded-growth of PLLA block copolymers with different corona-forming blocks.

14.
Chem Sci ; 10(30): 7281-7289, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31588298

RESUMO

Polymers with a phosphorus-boron main chain have attracted interest as novel inorganic materials with potentially useful properties since the 1950s. Although examples have recently been shown to be accessible via several routes, the materials reported so far have been limited to P-mono(organosubstituted) materials, [RHPBH2] n , containing P-H groups. Here we report a general route for the post-polymerisation modification of such polyphosphinoboranes giving access to a large range of previously unknown examples featuring P-disubstituted units. Insertion of alkenes, R'CH[double bond, length as m-dash]CH2 into the P-H bonds of poly(phenylphosphinoborane), [PhHPBH2] n was facilitated by irradiation under UV light in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPAP) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under benchtop conditions giving high molar mass, air-stable polymers [PhR'PBH2] n with controlled functionalisation and tunable material properties. The mechanistic explanation for the favourable effect of the addition of TEMPO was also investigated and was proposed to be a consequence of reversible binding to radical species formed from the photolysis of DMPAP. This new methodology was also extended to the formation of crosslinked gels and to water-soluble bottlebrush copolymers showcasing applicability to form a wide range of polyphosphinoborane-based soft materials with tunable properties.

15.
Chemistry ; 25(59): 13484-13490, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31415126

RESUMO

The controlled formation of complex and functional 1-, 2-, and 3D hierarchical assemblies from molecular building blocks represents a key current challenge. Herein, we report the use of a seeded growth approach for a series of perylenediimide-based molecules (PDIs 1-4) to access otherwise inaccessible self-assembly pathways that yield complex hierarchical structures. The key to the new approach is to use hetero-seeds which possess a different composition and morphology from that of the molecular building block. For example, a nanotube seed (from PDI 3) and a microribbon seed (from PDI 4) were found to initiate different self-assembly pathways for PDI 1, which normally assembles to yield nanocoils. This led to the formation of unprecedented 3D scroll-like and scarf-like hierarchical nanostructures, respectively. Also, the hetero-seeds from PDI 3 initiate hidden self-assembly pathways of PDI 2 to generate 1D tubular heterojunctions. Significantly, this new strategy offers new opportunities to create emergent and functional hierarchical and complex structures from small molecule precursors.

16.
Nat Commun ; 10(1): 2786, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31243267

RESUMO

Catalytic chemistry that involves the activation and transformation of main group substrates is relatively undeveloped and current examples are generally mediated by expensive transition metal species. Herein, we describe the use of inexpensive and readily available tBuOK as a catalyst for P-P and P-E (E = O, S, or N) bond formation. Catalytic quantities of tBuOK in the presence of imine, azobenzene hydrogen acceptors, or a stoichiometric amount of tBuOK with hydrazobenzene, allow efficient homodehydrocoupling of phosphines under mild conditions (e.g. 25 °C and < 5 min). Further studies demonstrate that the hydrogen acceptors play an intimate mechanistic role. We also show that our tBuOK catalysed methodology is general for the heterodehydrocoupling of phosphines with alcohols, thiols and amines to generate a range of potentially useful products containing P-O, P-S, or P-N bonds.

17.
Nat Commun ; 10(1): 1370, 2019 03 26.
Artigo em Inglês | MEDLINE | ID: mdl-30914640

RESUMO

The divalent carbene carbon centre in cyclic (alkyl)(amino)carbenes (CAACs) is known to exhibit transition-metal-like insertion into E-H σ-bonds (E = H, N, Si, B, P, C, O) with formation of new, strong C-E and C-H bonds. Although subsequent transformations of the products represent an attractive strategy for metal-free synthesis, few examples have been reported. Herein we describe the dehydrogenation of phosphine-boranes, RR'PH·BH3, using a CAAC, which behaves as a stoichiometric hydrogen acceptor to release monomeric phosphinoboranes, [RR'PBH2], under mild conditions. The latter species are transient intermediates that either polymerise to the corresponding polyphosphinoboranes, [RR'PBH2]n (R = Ph; R' = H, Ph or Et), or are trapped in the form of CAAC-phosphinoborane adducts, CAAC·H2BPRR' (R = R' = tBu; R = R' = Mes). In contrast to previously established methods such as transition metal-catalysed dehydrocoupling, which only yield P-monosubstituted polymers, [RHPBH2]n, the CAAC-mediated route also provides access to P-disubstituted polymers, [RR'PBH2]n (R = Ph; R' = Ph or Et).

18.
Chem Sci ; 10(8): 2280-2284, 2019 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-30881653

RESUMO

Self-seeding is a process unique to polymer crystals, which consist of regions of different chain packing order and different crystallinity. Here we report the synergistic self-seeding behaviour of pairs of core-crystalline block copolymer (BCP) micelle fragments and show how this strategy can be employed to control the morphology of these BCP comicelles. Each micelle fragment has a critical dissolution temperature (T c), and unimers of each BCP have a characteristic epitaxial growth rate. The T c value affects the dissolution sequence of the fragments upon heating, while the unimer growth rate affects the growth sequence upon cooling. By carefully choosing micelle fragments having different T c values as well as growth rates, we could prepare patchy comicelles and block comicelles with uniform and controllable length. This synergistic self-seeding strategy is a simple yet effective route to control both length and morphology of core-crystalline comicelles.

19.
ACS Nano ; 13(4): 3858-3866, 2019 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-30794379

RESUMO

Block copolymer self-assembly has enabled the creation of a range of solution-phase nanostructures with applications from optoelectronics and biomedicine to catalysis. However, to incorporate such materials into devices a method that facilitates their precise manipulation and deposition is desirable. Herein we describe how optical tweezers can be used to trap, manipulate, and pattern individual cylindrical micelles and larger hybrid micellar materials. Through the combination of TIRF imaging and optical trapping we can precisely control the three-dimensional motion of individual cylindrical block copolymer micelles in solution, enabling the creation of customizable arrays. We also demonstrate that dynamic holographic assembly enables the creation of ordered customizable arrays of complex hybrid block copolymer structures. By creating a program which automatically identifies, traps, and then deposits multiple assemblies simultaneously we have been able to dramatically speed up this normally slow process, enabling the fabrication of arrays of hybrid structures containing hundreds of assemblies in minutes rather than hours.

20.
J Am Chem Soc ; 141(7): 2894-2899, 2019 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-30726071

RESUMO

We describe a new class of inorganic polymeric materials featuring a main chain consisting of PV-O bonds and aryl side groups, which was obtained with >70 repeat units by ring-opening polymerization of cyclic phosphonates. This monomer-polymer system was found to be dynamic in solution enabling selective depolymerization under dilute conditions, which can be tuned by varying the substituents. The polymers show high thermal stability to weight loss and can be easily fabricated into self-standing thin films. Structural characterizations of the cyclic 6- and 12-membered ring precursors are also described.

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