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The design of a hybrid one-pot tandem protocol through the combination of biodeoximations (promoted by laccase from Trametes versicolor) and s-block polar organometallics (RLi/RMgX) in aqueous media, at room temperature and under air is reported.

The one-pot/two-step combination of enzymes and polar organometallic chemistry in aqueous media is for the first time presented as a proof-of-concept study. The unprecedented combination of the catalytic oxidation of secondary alcohols by the system laccase/TEMPO with the ultrafast addition (3 s reaction time) of polar organometallic reagents (RLi/RMgX) to the in situ formed ketones, run under air at room temperature, allows the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions (up to 96%).

A photo-responsive linear poly(azobenzene) with an alternating sequence of azobenzene switching units connected by trisiloxane linkers was synthesised via step-growth polycondensation. By its design, the polymer features a high chromophore load (45 wt%) and a large number (≈130) of photoswitching units per chain. The ensuing photoisomerisation upon UV irradiation with 365 nm light was studied in several solvents and compared to the corresponding free azobenzene siloxane congener. Efficient E → Z isomerisation with high conversion yields was observed for the polymeric and isolated azobenzenes alike. In the slightly polar solvents tetrahydrofuran (THF) and chloroform, this resulted in a photo-induced decrease in solvodynamic volume of 22% (THF) and 32% (chloroform). In n-hexane, however, a light-triggered collapse of the solvated polymer coil lead to a globular non-solvated form with a 70% decrease in volume. Ultrafast transient electronic absorption measurements showed that the underlying excited-state reaction pathways for the azobenzene units in the polymer main chain are essentially similar to those of the analogous single azobenzene in solution. The data suggest a sequential deactivation via ultrafast internal conversion from the initially excited S2 state to the S1 state, followed by intramolecular vibrational redistribution in the S1 state, and subsequent E → Z isomerisation and deactivation to the electronic ground state. These processes are slowed down only moderately for the main chain azobenzene units compared to the free azobenzene in solution and conform to the accepted scenario for unsubstituted azobenzene. The results explain the efficient, nearly unconstrained isomerisation of the embedded molecular switching units that is highly unusual for a main chain azobenzene polymer. Due to the unique combination of a high chromophore load and large number of photo-switchable units in the main chain in a regular alternating architecture, coupled with a high conversion yield, the poly(azobenzene-alt-trisiloxane) should find applications as photo-responsive material, in particular when large switching amplitudes are essential.

A tandem protocol to access tertiary alcohols has been developed which combines the organocatalytic oxidation of secondary alcohols to ketones followed by their chemoselective addition by several RLi reagents. Reactions take place at room temperature, under air and in aqueous solutions, a trio of conditions that are typically forbidden in polar organometallic chemistry.

S.E.G.-G. and J.G.A thank the Spanish MINECO and MIC (Project PID2020-113473GB-I00). J.G.-A. thanks: i) the Fundación BBVA for the award of a “Beca Leonardo a Investigadores y Creadores Culturales 2017”; and ii) PhosAgro/UNESCO/IUPAC for the award of a “Green Chemistry for Life Grant”. A.P.S is indebted to Spanish MINECO (Project CTQ2014-56345-P, CTQ2017-88357-P, and RYC-2012-09800), and Gobierno del Principado de Asturias (FICYT, Project FC-15-GRUPIN14-106) for financial support. E.H. acknowledges the SNF (188573) and the EPSRC (EP/S020837/2) for their generous financial support

An efficient and selective N-functionalization of amides is first reported via a CuI-catalyzed Goldberg-type C–N coupling reaction between aryl iodides and primary/secondary amides run either in Deep Eutectic Solvents (DESs) or water as sustainable reaction media, under mild and bench-type reaction conditions (absence of protecting atmosphere). Higher activities were observed in an aqueous medium, though the employment of DESs expanded and improved the scope of the reaction to include also aliphatic amides. Additional valuable features of the reported protocol include: (i) the possibility to scale up the reaction without any erosion of the yield/reaction time; (ii) the recyclability of both the catalyst and the eutectic solvent up to 4 consecutive runs; and (iii) the feasibility of the proposed catalytic system for the synthesis of biologically active molecules.

Atom Transfer Radical Polymerisation (ATRP) is one of the most important techniques to synthesize well-defined polymers with predetermined molecular weight, designed microstructure and tailor-made functionalities. Although ATRP has been extensively studied in a variety of common Volatile Organic Solvents (VOCs) and water, there is significantly less work done using fashionable and environmentally friendly Deep Eutectic Solvents (DESs). Aiming to develop greener ATRP routes by allowing the recycling of the employed transition metal catalyst, we herein present the homogeneous and heterogeneous Cu-catalysed ARGET variation of the ATRP processes using methyl methacrylate (MMA) as the model monomer and a DES as a green solvent. The homogeneous ARGET ATRP was performed employing CuCl2 as a catalyst and FDA-approved tin(II) 2-ethylhexanoate [Sn(EH)2] as a reducing ARGET agent, under an air atmosphere. The polymerisations proceeded in a controlled/“living” fashion according to reversible deactivation radical polymerisation (RDRP) standards. Heterogeneous ARGET ATRP was carried out by using a DES-insoluble Cu(II) Metal–Organic Framework (MOF) as a recyclable catalyst in the absence of organic ligands, employing Sn(EH)2 as a reducing agent, under an air atmosphere. Under these experimental conditions, well-defined poly(methyl methacrylate) (PMMA) was obtained (Đ ≈ 1.2) under controlled RDRP conditions. Importantly, both the MOF catalyst and DES were successfully recycled up to 6 consecutive catalytic cycles to synthesize PMMAs with comparable macromolecular features and yields.

We herein report the formation of two complex nanostructures, toroidal micelles and bicontinuous nanospheres, by the self-assembly of the single structurally simple crystalline-b-coil diblock copolymer poly[bis(trifluoroethoxy)phosphazene]-b-poly(styrene), PTFEP-b-PS, in one solvent (THF) and without additives. The nature of these nanostructures in solution was confirmed by DLS and cryo-TEM experiments. The two morphologies are related by means of a new type of reversible morphological evolution, bicontinuous-to-toroidal, triggered by changes in the polymer concentration. WAXS experiments showed that the degree of crystallinity of the PTFEP chains located at the core of the toroids was higher than that in the bicontinuous nanospheres, thus indicating that the final morphology of the aggregates is mostly determined by the ordering of the PTFEP core-forming blocks.

We herein reports the solid-state synthesis of pure and doped lanthanide oxides by using polymeric materials (chitosan and polystyrene- co -poly(4-vinylpyridine), PS-co-P4VP) as a solid template. Lanthanide nanomaterials are prepared in two-step methodology combining both solution and solid procedures. The first involves the synthesis of macromolecular complexes Chitosan·[M(NO 3 ) 3 //M′(NO 3 ) 3 ] and PS- co -P4VP·[M(NO 3 ) 3 //M′(NO 3 ) 3 ] (M = La, Pr; M′ = Eu); and the second consists in the pyrolysis at 800 °C of the as-prepared solid macromolecular complexes. The pyrolytic products were characterized by X-ray diffraction, SEM-EDS, TEM, and HR-TEM. Whereas similar particle size distribution in average ( ca. 25 nm) was observed with both polymer templates, a higher degree of crystallinity was obtained by using PS- co -P4VP. Importantly, the emission luminescent intensity of the doped pyrolytic oxides, La 2 O 3 //Eu 2 O 3 and PrO 1,83 //Eu 2 O 3 , is not quenched despite the presence of dopant. Thus, the as-prepared doped oxides exhibit an enhanced Eu 3+ emission originated from the 5 D 0 → 7 F n (n = 1, 2, 3, 4) transitions, which is more intense for the PS- co -P4VP template. This synthetic methodology base on the pyrolysis of polymeric complexes can be considered as a general and straightforward methodology leading to pure and Eu 3+ -doped nanostructured lanthanide oxide.

L.C. and J.G.A thank the Spanish MINECO (Project CTQ2016-75986-P and CTQ2016-81797-REDC). A.F. A.S.-C., G.A.C and A.P.Sare indebted to Spanish MINECO (Project CTQ2014-56345-P,CTQ2017-88357-P, and RYC-2012-09800), and Gobierno delPrincipado de Asturias (FICYT, Project FC-15-GRUPIN14-106) forfinancial support. A.P.S. is also grateful to the COST action SmartInorganic Polymers (SIPs-CM1302 – http://www.sips-cost.org/home/index.html), and Spanish MEC for the Juan de la Cierva and Ramón y Cajal programs. J. G.-A. thanks: i) the Fundación BBVAfor the award of a “Beca Leonardo a Investigadores y Creadores Culturales 2017”;[33]and ii) PhosAgro/UNESCO/IUPAC for the awardof a “Green Chemistry for Life Grant”. This work was carried out under the framework of the project “Development of Sustainable Synthetic Processes in Unconventional Solvents for the Preparationof Molecules of Pharmaceutical Interest” realized with the contribution of Fondazione Puglia, which is gratefully acknowledged by L.C. and V.C.

Producción Científica, The random phosphazene copolymer {[N=P((CH2)7-Br)Ph]0,5[N=PMePh]0,5}n (2) and the block copolyphosphazene {[N=P((CH2)7-Br)Ph]25[N=PMePh]20}-b-[N=P(O2C12H8)]55 (5), having a branch with two randomly distributed units, have been synthesized and used as precursors for the stannyl derivatives {[N=P((CH2)7-SnBu2An)Ph]0,5[N=PMePh]0,5}n (3) and {[N=P((CH2)7-SnBu2An)Ph]25[N=PMePh]20}-b-[N=P(O2C12H8)]55 (6, An = p-MeOC6H4). Polymers 3 and 6 were tested as recyclable tin reagents in the Stille cross-coupling reaction with C6H5I, using various Pd catalysts and different experimental conditions. Polymer 6 can be recycled without significant release of tin, but its efficiency decreased after three consecutive cycles. This effect was explained by studying the self-assembly of the polymer under the same conditions used for the catalytic experiments, which evidenced the progressive coalescence of the polymeric vesicles (polymersomes) leading to stable and bigger core-shell aggregates by the attraction of the [N=P(O2C12H8)] rich membranes, thus decreasing the accessibility of the tin active centers., 2017-12-15, Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA302U13), Ministerio de Economía, Industria y Competitividad (CTQ2014-56345), Ministerio de Economía, Industria y Competitividad (CTQ2013-48406-P), Universidad de Oviedo (Project UNOV-13-EMERG-GIJON-08)

Determination of stoichiometries between engineered nanoparticles and species attached to their surface after chemical functionalization or interaction with biological media has been a hotspot during the last years, still unsatisfactory solved. Herein we propose a new approach only requiring for a simple mass spectrometric sulfur isotope ratio measurement in the final solution. Of course, enriched 34S isotope has to be previously introduced in the engineered nanoparticle structure. Conversely to existing methodologies, mostly based on relative analyte measurements, proposed method does not require any previous knowledge of the molecule concentration in the starting solution. Such rather generic approach can be applied to study physical and/or chemical interactions between any sulfur-containing molecule and a wide variety of engineered nanoparticles containing sulfur as well, either in their own core-shell structure or in the ligand used for their surface functionalization (e.g. any thiol-derivative). In this paper, an inexpensive standard synthetic procedure was carried out to incorporate the required stable isotopic 34S into the ZnS shell of CdSe quantum dots (QDs). Such isotopically enriched nanoparticles were then successfully applied to the quantitative assessment of stoichiometries between QDs and different target biomolecules, such as surface-functionalizing molecules (e.g. biotin) and proteins (e.g. bovine serum albumin). Of course, any biological conclusion and/or optimized bioconjugation conditions obtained using such isotopically enriched QDs analogues could be easily translated to nanoassemblies obtained using regular non-enriched QDs since they are chemically and physically identical.

In each of the crystal structures of the two title compounds, two mol­ecules are found in the asymmetric unit. Individual mol­ecules are linked by inter­molecular O—H⋯O hydrogen bonding and show significant differences in the torsions about the N=N bond and the dihedral angle between the benzene rings., The title compounds {systematic names (E)-[diazene-1,2-diylbis(3,1-phenyl­ene)]bis­(di­methyl­silanol) and (E)-[diazene-1,2-diylbis(4,1-phenyl­ene)]bis­(di­methyl­silanol)}, both of the sum formula C16H22N2O2Si2, were obtained by transmetallation of the respective bis-stannylated azo­benzenes with di­chloro­dimethyl­silane and esterification followed by hydrolysis. The asymmetric unit of 3,3′-diazenediylbis[dimeth­yl(phen­yl)silanol] (with the silanol functional group in a meta position) consists of two mol­ecules, of which one occupies a general position, whereas the second is located on a centre of inversion. In 4,4′-diazenediylbis[dimeth­yl(phen­yl)silanol] (with the silanol functional group in a para position) likewise two mol­ecules are present in the asymmetric unit, but in this case both occupy general positions. Differences between all mol­ecules can be found in the torsions about the N=N bond, as well as in the dihedral angles between the benzene rings. In both structures, inter­molecular O—H⋯O hydrogen bonding is observed, leading to the formation of layers parallel to (01-1) for (I) and to chains parallel to the a axis for (II).

Despite their ubiquitous presence in synthesis, the use of polar organolithium reagents under environmentally benign conditions constitutes one of the greatest challenges in sustainable chemistry. Their high reactivity imposes the use of severely restrictive protocols (e.g., moisture- and oxygen-free, toxic organic solvents, inert atmospheres, low temperatures, etc.). Making inroads towards meeting this challenge, a new air- and moisture-compatible organolithium-mediated methodology for the anionic polymerization of different olefins (e.g., styrenes and vinylpyridines) was established by pioneering the use of deep eutectic solvents (DESs) as an eco-friendly reaction medium in this type of transformation. Fine-tuning of the conditions (sonication of the reaction mixture at 40 °C in the absence of protecting atmosphere) along with careful choice of components of the DES [choline chloride (ChCl) and glycerol (Gly) in a 1:2 ratio] furnished the desired organic polymers (homopolymers and random copolymers) in excellent yields (up to 90 %) and low polydispersities (IPD 1.1-1.3). Remarkably, the in situ-formed polystyril lithium intermediates exhibited a great resistance to hydrolysis in the eutectic mixture 1ChCl/2Gly (up to 1.5 h), hinting at an unexpected high stability of these otherwise highly reactive organolithium species in these unconventional reaction media. This unique stability can be exploited to create well defined block-copolymers.

A variety of surfaces are patterned with precisely defined cylindrical micelles

The preparation of long-term-stable giant unilamellar vesicles (GUVs, diameter ≥ 1000 nm) and large vesicles (diameter ≥ 500 nm) by self-assembly in THF of the crystalline-b-coil polyphosphazene block copolymers [N=P(OCH2CF3)2 ]n-b-[N=PMePh]m (4 a: n=30, m=20; 4 b: n=90, m=20; 4 c: n=200, m=85), which combine crystalline [N=P(OCH2CF3)2] and amorphous [N=PMePh] blocks, both of which are flexible, is reported. SEM, TEM, and wide-angle X-ray scattering experiments demonstrated that the stability of these GUVs is induced by crystallization of the [N=P(OCH2CF3)2] blocks at the capsule wall of the GUVS, with the [N=PMePh] blocks at the corona. Higher degrees of crystallinity of the capsule wall are found in the bigger vesicles, which suggests that the crystallinity of the [N=P(OCH2CF3)2] block facilitates the formation of large vesicles. The GUVs are responsive to strong acids (HOTf) and, after selective protonation of the [N=PMePh] block, they undergo a morphological evolution to smaller spherical micelles in which the core and corona roles have been inverted. This morphological evolution is totally reversible by neutralization with a base (NEt3), which regenerates the original GUVs. The monitoring of this process by dynamic light scattering allowed a mechanism to to be proposed for this reversible morphological evolution in which the block copolymer 4 a and its protonated form 4 a(+) are intermediates. This opens a route to the design of reversibly responsive polymeric systems in organic solvents. This is the first reversibly responsive vesicle system to operate in organic media.

Esta Tesis Doctoral se enmarca en el campo de la Química de Polímeros Inorgánicos, más concretamente en el de la química de Polímeros Inorgánicos de bloques. En ella se describe la síntesis y auto-organización de copolifosfacenos de dos bloques del tipo polifosfaceno-b-polifosfaceno y polifosfaceno-b-poliestireno. La tesis está dividida en dos Capítulos donde se describen respectivamente la síntesis y auto-organización de este tipo de macromoléculas. En el Capítulo 1 se describe la síntesis y auto-organización de copolifosfacenos de bloques inorgánicos e híbridos con estructura helicoidal intrínseca o inducida. En primer lugar, se presenta una nueva ruta de síntesis para los copolifosfacenos de bloques híbridos del tipo polifosfaceno-b-poliestireno basada en el empleo de iniciadores bifuncionales del tipo Li-C6H4-PPh2 capaces de iniciar la polimerización aniónica y catiónica “viva” del estireno y de las N-Sililfosforaniminas respectivamente, para obtener los copolímeros deseados con un alto control del grado de polimerización y bajos índices de polidispersidad. Así, se sintetizaron copolifosfacenos de bloques que combinan un segmento flexible y amorfo (PSm) con otro que posee helicidad intrínseca ([N=P(R-O2C20H12)]n). Además, se sintetizaron copolifosfacenos de bloques del tipo polifosfaceno-b-polifosfaceno dotados de un bloque [N=P(O-C6H4-CO2H)2]n, lo que permitió estudiar los procesos de inducción helicoidal en presencia de una molécula quiral (R-(+)-1-feniletilamina). Durante la auto-organización de ambos copolímeros de bloques en disolución se observó la transferencia de información quiral desde las cadenas poliméricas hasta las nanoestructuras, observándose distintas estructuras helicoidales tales como vesículas, toroides, semi-toroides, boles, cúpulas, tubos y redes 2D, dependiendo de la longitud del bloque helicoidal y la concentración del copolímero de bloques en la disolución inicial. En el Capítulo 2 se describe la síntesis y auto-organización de los copolímeros de bloques con un segmento cristalino [N=P(OCH2CF3)2]n-b-PSm. La auto-organización de estos materiales mostró una fuerte dependencia de las morfologías obtenidas con la concentración inicial de copolímero de bloques en la disolución. Así, variando esta concentración se pudieron obtener nanoestructuras muy bien definidas con morfologías que vas desde esféricas, a esferas bicontínuas, nano-toroides, redes de cilindros y, finalmente, estructuras de doble-capa tipo vesícula. En todas ellas el segmento fosfacénico cristalino actúa de núcleo y el grado de cristalinidad de dicho bloque controla la morfología final, encontrándose que mientras en la morfología esférica el bloque [N=P(OCH2CF3)2] es prácticamente amorfo, en las redes de cilindros el grado de cristalinidad es muy alto (14%). Esta variedad de estructuras permitió describir una nueva transición morfológica reversible entre esferas bi-continuas y toroides, que no había sido descrita previamente en la bibliografía.

The sequential living polymerization of N-silylphosphoranimines for the synthesis of polyphosphazene-b-polyphosphazene diblock copolymers (PP-b-PP) has been studied both experimentally and theoretically. For the experiments, BrMe2P═N–SiMe3, [Cl3P═N═PCl3][X] (X = PCl6–, Cl–), Cl3P═N–SiMe3, ClMe2P═N–SiMe3, and [Me3P═N═PMe2Cl]+ were used as representative model reagents. Density functional theory (DFT) calculations in the gas phase adjusted for solvent effects on ClMe2P═N–SiMe3, [Cl3P═N═PCl3]+, Cl3P═N–SiMe3, and ClMe2P═N–SiMe3 confirmed the experimental observations. The results have shown the necessity of starting with mono-end-capped initiators to avoid the formation of triblock chains. It was also demonstrated that the nature of the nucleophilic N-silylphosphoranimines and the electrophilic cationic end groups of the living polyphosphazenes strongly affects the polymerization reaction, imposing limits to its synthetic potential. Thus, good electron donor N-silylphosphoranimines, i.e. XR2P═N–SiMe3, react b...

The unexpected finding that the complex [Au(PPh3)2]PF6 (C1) catalyses the specific hydration of 1-octyne, (p-phenoxyphenyl)acetylene, phenylacetylene, (p-chlorophenyl)acetylene and benzylacetylene at 100 °C in the presence of H2SO4 and THF or methanol as solvents, specially using microwave radiation, led to the first gold(I) recyclable catalysts for this reaction. The phosphazene polymeric framework of idealised formula {[NP(O2C12H8)]0.85[NP(OC6H4PPh2)2 (AuPF6)0.5]0.15}n (C2), and the newly synthesised cyclomatrix material of idealised formula {[N3P3(OC6H4PPh2)6](AuPF6)3.5}n (C3), both having cationic [–Ph2P–Au+–PPh2–] cross-linking sites, catalysed the complete hydration of terminal alkynes at 100 °C and 150 °C and could be used six and four times respectively without significant loss of activity. The mechanism of the catalytic system is based on the initial reversible displacement of one anchoring O–C6H5–PPh2 group from the [–Ph2P–Au+–PPh2–] cross-linking sites by an alkyne molecule. Using microwave radiation, the hydration of (p-phenoxyphenyl)acetylene, phenylacetylene, (p-chlorophenyl)acetylene and benzylacetylene can be completed in 5 min to 2 h in the absence of any gold(I) catalyst.

Nanostructure luminescent ZnO and SnO2 materials are prepared by a two-step solid-state method based on the solution preparation of the macromolecular precursors ZnCl2·Chitosan and SnCl2·Chitosan having different ratios (1:1, 1:5 and 1:10), their pyrolysis under air at 800 °C. The pyrolytic ZnO and SnO2 nanomaterials show a dependence of the particle size, morphology and luminescent properties with the ratio [metal/polymer] in the MCl2·Chitosan precursors. Thus, ZnO semiconductor materials exhibit luminescence spectra with several emission at 440 nm corresponds to a radiative transition of an electron from the shallow donor level of oxygen vacancies, and the zinc interstitial, to the valence band. On the other hand, the photoluminescence spectrum of the nanostructured SnO2 shows an intense blue luminescence at a wavelength of 420 nm which may be attributed to oxygen-related defects that have been introduced during the growth process of the nanoparticles. Additionally, whereas SnO2 was successfully incorporated into SiO2 structure (SnO2//SiO2) by pyrolysis of solid-state mixtures of the precursors SnCl2·Chitosan in the presence of SiO2, the same reaction carried out with ZnCl2·Chitosan precursors led to a mixture of Zn2SiO4 and SiO2. Thus, this new methodology yields nanostructured semiconductor materials, ZnO and SnO2, suitable for optoelectronic and sensor solid-state devices.

We describe a new and very versatile method to place chosen chemical functionalities at the edge of the pores of macroporous materials. The method is based on the synthesis and self-assembly of inorganic block copolymers (BCPs) having chiral rigid segments bearing controllable quantities of randomly distributed functional groups. The synthesis of a series of optically active block copolyphosphazenes (PP) with the general formula [N=P(R-O2C20H12)(0.9)(FG)(0.2)]n-b-[N=PMePh]m (FG=-OC5H4N (6), -NC4H8S (7), and -NC4H8O (8)), was accomplished by the sequential living cationic polycondensation of N-silylphosphoranimines, using the mono-end-capped initiator [Ph3P=N=PCl3][Cl] (3). The self-assembly of the phosphazene BCPs 6-8 led to chiral porous films. The functionality present on those polymers affected their self-assembly behaviour resulting in the formation of pores of different diameters (D(n)=111 (6), 53 (7) and 77 nm (8)). The specific functionalisation of the pores was proven by decorating the films with gold nanoparticles (AuNPs). Thus, the BCPs 6 and 7, having pyridine and thiomorpholine groups, respectively, were treated with HAuCl4, followed by reduction with NaBH4, yielding a new type of block copolyphosphazenes, which self-assembled into chiral porous films specifically decorated with AuNPs at the edge of the pores.

A series of optically active helical polyphosphazene block copolymers of general formula R-[N=P(O2C20H12)]n-b-[N=PMePh]m (R-7 a-c) was synthesized and characterized. The polymers were prepared by sequential living cationic polycondensation of N-silylphosphoranimines using the mono-end-capped initiator [Ph3 P=N=PCl3][PCl6] (5) and exhibit a low polydispersity index (ca. 1.3). The temperature dependence of the specific optical activity ([α]D) of R-7 a,b relative to that for the homopolymers R-[N=P(O2C20H12)]n (R-8 a) and the R/S analogues (R/S-7 a,b), revealed that the binaphthoxy-phosphazene segments induce a preferential helical conformation in the [N=PMePh] blocks through a "sergeant-and-soldiers" mechanism, an effect that is unprecedented in polyphosphazenes. The self-assembly of drop-cast thin films of the chiral block copolymer R-7 b (bearing a long chiral and rigid R-[N=P(O2C20H12)] segment) evidenced a transfer of helicity mechanism, leading to the formation of twisted morphologies (twisted "pearl necklace"), not observed in the nonchiral R/S-7 b. The chiral R-7 a and the nonchiral R/S-7 a, self-assemble by a nondirected morphology reconstruction process into regular-shaped macroporous films with chiral-rich areas close to edge of the pore. This is the first nontemplate self-assembly route to chiral macroporous polymeric films with pore size larger than 50 nm. The solvent annealing (THF) of these films leads to the formation of regular spherical nanostructures (ca. 50 nm), a rare example of nanospheres exclusively formed by synthetic helical polymers.