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9 protocols using cd2cl2

1

Solvent Purification and Chemical Reagents

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Dichloromethane, tetrahydrofuran (THF), and N,N-dimethylformamide (DMF) were purified
by passage through a solvent purification system (JC Meyer Solvent
Systems) and used as anhydrous solvents. The deuterated solvents (CDCl3, CD2Cl2, DMSO-d6) were products of Cambridge Isotopes Laboratories. All other
reagents and solvents, tributylphosphine (PBu3, Alpha Aesar),
trimethylphosphine (PMe3, Alpha Aesar), 2-chloroethanol
(Alpha Aesar), thionyl chloride (SOCl2, Aldrich), potassium
thioacetate (KSAc, Alpha Aesar), anhydrous methanol (Alpha Aesar),
2,2-dimethoxy-2-phenylacetophenone (DMPA, Aldrich), anhydrous dimethyl
sulfoxide (ACROS, DMSO), Alexa Fluor 488 azide (A488, Life Technologies),
copper bromide (CuBr, Aldrich), N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA, Aldrich), and ultrapure
water (molecular biology grade, Quality Biological, Inc.) were used
as received.
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2

Deoxygenation and Purification Protocols

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All commercially obtained reagents were used
as received unless otherwise noted. All solvents were stored in a
≤1 ppm O2 drybox prior to use. Acetone packed under
nitrogen was purchased from Burdick & Jackson (water content <0.5%).
Cyclohexene (Aldrich, 99%) was freshly distilled over sodium metal
under argon and stored in a predried glass bottle. [Ir(1,5-COD)Cl]2 (STREM), tris(dodecyl)amine (Aldrich, 97%), trioctylphosphine
(Aldrich, 97%), and tributylamine (Aldrich, ≥99.5%) were stored
in a drybox. Solutions (1.0 M) of proton sponge (Aldrich) in acetone
were freshly made. Acidic γ-Al2O3 (Aldrich)
with a surface area of 155 m2/g was dried at 160 °C
for 24 h and stored in the drybox prior to use. CD2Cl2 (Cambridge Isotope Laboratories) from 1 mL glass ampoules
were transferred into the drybox for NMR sample preparation. H2 gas was purchased from General Air in >99.5% purity and
passed
through O2 and H2O scavenging traps (Trigon
Technologies) before use to pressurize Fisher-Porter (FP) bottle reactors
(vide infra).
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3

Synthesis of Lanthanide-Manganese Compounds

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Reactions performed under an inert atmosphere were carried out in oven-dried glassware in a glovebox under a nitrogen atmosphere. Anhydrous dichloromethane and diethyl ether were purified by sparging with nitrogen for 15 min and then passing under nitrogen pressure through a column of activated A2 alumina (Zapp’s). CD2Cl2 was purchased from Cambridge Isotope Laboratories, dried over calcium hydride, then degassed by three freeze–pump–thaw cycles, and vacuum-transferred prior to use. 1H NMR spectra were recorded on a Varian 300 MHz instrument, with shifts reported relative to the residual solvent peak. 19F NMR spectra were recorded on a Varian 300 MHz instrument, with shifts reported relative to the internal lock signal. Elemental analyses were performed by Robertson Microlit Laboratories. All commercial chemicals were used as received. Dysprosium trifluoromethanesulfonate (Dy(OTf)3) and decamethylferrocene were purchased from Strem, and yttrium trifluoromethanesulfonate (Y-(OTf)3) was purchased from Aldrich. [LDyMn3O4(OAc)3(DMF)2]-[OTf]5b (link) and [LYMn3O4(OAc)3(DMF)2][OTf]5c (link) were prepared according to previously published procedures.
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4

Inert Atmosphere Synthesis and Characterization

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All air- and moisture-sensitive
manipulations were carried out using a standard high vacuum line,
Schlenk, or cannula techniques or in an MBraun inert atmosphere drybox
containing an atmosphere of purified dinitrogen. All solids were dried
under a high vacuum in order to be brought into the glovebox. Solvents
for air- and moisture-sensitive manipulations were dried and deoxygenated
using a Glass Contour Solvent Purification System (Pure Process Technology,
LLC) and stored over activated 4 Å molecular sieves (Fisher Scientific)
prior to use. Deuterated solvents for NMR spectroscopy were purchased
from Cambridge Isotope Laboratories, distilled from sodium metal (C6D6) or CaH2 (CD2Cl2) after three freeze–pump–thaw cycles, and stored in
the glovebox over activated 3 Å molecular sieves. Uranyl chloride
trihydrate was purchased from International Bio-Analytical Industries
and used as received. All the remaining chemicals were purchased from
commercial sources (Fisher Scientific, VWR, and Sigma-Aldrich) and
used without further purification. H2MesPDPPh,60 (link) H2Cl2PhPDPPh,62 (link) and [UO2Cl2(THF)2]275 (link) were synthesized following reported procedures.
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5

Synthesis and Characterization of Mn(V) Complex

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The compound MnV(O)(TBP8Cz) was synthesized according to a published procedure.24 (link) All other reagents were commercially available and purchased at the highest level of purity and used as received unless otherwise specified here. The oxonium acid HBArF ([H(OEt2)2]+[B(C6F5)4]) was synthesized according to a published procedure.52 The substrate 9,10-dihydro-10-methylacridine (AcrH2) was synthesized according to a published procedure.41 (link) The substrates xanthene (Xn) and 9,10-dihydroanthracene (DHA) were purchased from Sigma-Aldrich and recrystallized at least three times from ethanol. The substrate 1,4-cyclohexadiene (CHD) was purchased from Sigma-Aldrich and purified by running through an alumina pipette column immediately before use. The deuterated substrate xanthene-d2 was synthesized according to a published procedure.53 (link) Deuterated solvents (CDCl3 and CD2Cl2) for NMR were purchased from Cambridge Isotopes, Inc.
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6

Synthesis of Heterobimetallic Complexes

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The
heterobimetallic complexes, [ClNi(o-Ph2P-C6H4)3As]Cl,31 (link) ClNi(o-Ph2P-C6H4)3SbCl,32 (link) ClAu(o-iPr2P-C6H4)2BiCl,33 (link) ClPt(o-Ph2P-C6H4)3SbCl,34 (link) and ClPd(o-Ph2P-C6H4)2SbCl2,35 (link) were prepared according to literature procedures.
[(CyNC)Pd(o-Ph2P-C6H4)2SbCl2][SbF6] and [ClPd(o-Ph2P-C6H4)3As]Cl are synthesized as follows. NiCl2 (anhydrous, 98%),
bis(1,5-cyclooctadiene)nickel (0) (Ni(COD)2, 98+%), Ph3Sb (97%), cyclohexyl isocyanide (CyNC, 98%), and AgSbF6 (99%) were purchased from Strem and used as received. CH2Cl2, Et2O, and tetrahydrofuran (THF)
were purchased from Fisher Chemical, and celite was purchased from
MilliporeSigma. CD2Cl2 and CDCl3 were
purchased from Cambridge Isotope Labs and used as received. CH2Cl2 was dried over alumina using a column-based
solvent purification system from MBraun. Et2O and THF were
refluxed under N2 over Na/K and distilled prior to use.
All precursor syntheses were carried out in air.
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7

Synthesis and Characterization of Glycine Polymers

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All the chemicals and solvents were purchased
from Sigma Aldrich and were used as received unless otherwise noted.
The solvents used for polymerization were further purified by using
alumina columns under argon protection. CD2Cl2 and CDCl3 were purchased from Cambridge Isotope laboratories. l-α-Phosphatidylcholine (PC) and liposome extrusion setup
were purchased from Avanti Polar Lipids. Polycarbonate membranes and
membrane filter support were purchased from EMD Millipore. Deionized
water used for DLS and SLS was further purified by a Nanopure Bioresearch
water purification system with a resistance of 17.8–17.9 MΩ·cm
from Barnstead Lab Water Products. 1H NMR was collected
by a Bruker AV-400 III spectrometer at 298 K and analyzed using Topspin
software. Chemical shifts (δ) given in parts per million (ppm)
were referenced to protio impurities. N-Decyl glycine-derived N-carboxyanhydride (De-NCA), N-butyl glycine-derived N-carboxyanhydride (Bu-NCA), and N-methoxyethyl
glycine-derived N-carboxyanhydride (MeOEt-NCA) monomers
were synthesized using a published procedure.34 (link)
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8

Inert Atmosphere Synthesis and NMR Characterization

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All manipulations were carried out in dry N2-filled gloveboxes (Vacuum Atmospheres Co., Hawthorne, CA) or under N2 atmosphere using standard Schlenk techniques unless otherwise noted. All solvents were of commercial grade and dried over activated alumina using a PPT Glass Contour (Nashua, NH) solvent purification system prior to use, and were stored over molecular sieves. All chemicals were from major commercial suppliers and used as received or after extensive drying. CD3CN and CD2Cl2 were purchased from Cambridge Isotope Laboratories (Tewksbury, MA, USA) and dried over 3 Å molecular sieves. 1 H, 13 C, 31 P and 19 F NMR spectra were collected on a 400 MHz Bruker spectrometer (Bruker, Billerica, MA, USA) and referenced to the residual protio-solvent signal 41 in the case of 1 H and 13 C. 31 P and 19 F NMR spectra were referenced and reported relative to H3PO4 and CCl3F, respectively, as external standards following the recommended scale based on ratios of absolute frequencies (Ξ). 42, 43 Chemical shifts (δ) are reported in units of ppm and coupling constants (J) are reported in Hz. All experiments were conducted at room temperature (298 K).
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9

Inert Atmosphere Synthesis and NMR Characterization

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All manipulations were carried out in dry N2-filled gloveboxes (Vacuum Atmospheres Co., Hawthorne, CA) or under N2 atmosphere using standard Schlenk techniques unless otherwise noted. All solvents were of commercial grade and dried over activated alumina using a PPT Glass Contour (Nashua, NH) solvent purification system prior to use, and were stored over molecular sieves. All chemicals were from major commercial suppliers and used as received or after extensive drying. CD3CN and CD2Cl2 were purchased from Cambridge Isotope Laboratories (Tewksbury, MA, USA) and dried over 3 Å molecular sieves. 1 H, 13 C, 31 P and 19 F NMR spectra were collected on a 400 MHz Bruker spectrometer (Bruker, Billerica, MA, USA) and referenced to the residual protio-solvent signal 41 in the case of 1 H and 13 C. 31 P and 19 F NMR spectra were referenced and reported relative to H3PO4 and CCl3F, respectively, as external standards following the recommended scale based on ratios of absolute frequencies (Ξ). 42, 43 Chemical shifts (δ) are reported in units of ppm and coupling constants (J) are reported in Hz. All experiments were conducted at room temperature (298 K).
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