microwave-mediated synthesis of bulky lanthanide porphyrin ... · microwave-mediated synthesis of...

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Supporting information for:

Microwave-mediated Synthesis of Bulky Lanthanide Porphyrin-

Phthalocyanine Triple-Deckers: Electrochemical and Magnetic

Properties

Hong-Guang Jin,*,†

Xiaoqin Jiang,‡ Irina Kühne,

§ Sylvain Clair,

# Valérie Monnier,

∆

Christophe Chendo,∆

Ghenadie Novitchi,≠

Annie K. Powell,*,§,¶

Karl M. Kadish,*,‡

Teodor Silviu Balaban*,†

† Aix-Marseille Université, CNRS UMR 7313, Centrale Marseille, Chirosciences,

Service 442, Avenue Escadrille Normandie-Niemen, F-13013 Marseille, France ‡ Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United

States § Institut für Anorganische Chemie, Karlsruhe Institute of Technology (KIT), Engesserstr.

15, D-76131 Karlsruhe, Germany #

Aix-Marseille Université, CNRS UMR 7334, Institut Matériaux Microélectronique

Nanosciences de Provence, F-13397 Marseille, Cedex 20, France ∆ Aix Marseille University, CNRS FR 1739, Spectropole, Avenue Escadrille Normandie

Niemen, F-13397 Marseille, Cedex 20, France ≠

CNRS, UPR3228, Laboratoire National des Champs Magnétiques Intenses, F-38042

Grenoble, Cedex 9, France ¶ Karlsruhe Institute of Technology, Institute for Nanotechnology, Hermann-von-

Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany

*Email: [email protected];

[email protected];

[email protected];

[email protected]

mailto:[email protected]

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Table of Contents

1. Materials, Methods and Instrumentation…………………………………...S3

2. Experimental Data

Synthetic procedures…………………………………………………………….S5

Figure S1. UV-vis-NIR absorption spectra of double-deckers 6ac………..S8

Figure S2 and S3. Mass spectra of TD-1 and TD-2 prepared following the

conventional procedure………………………………………………………….S9

Figure S4. UV-vis absorption spectra of TD-1TD-5 in PhCN……………..S10

Figure S5. UV-vis NIR absorption spectra of TD-1TD-4 in CHCl3………. S10

Figure S6. UV-vis absorption spectra of 7a/7b in CHCl3……………………S11

Figure S7S9. UV-vis spectral changes of TD-1, TD-3 and TD-4 during

the controlled first oxidation/reduction potential in PhCN containing 0.1 M

TBAP……………………………………………………………………………..S12

Figure S10. Out-of-phase susceptibility of Tb2 (TD-3) and Dy2 (TD-4) at

varying magnetic field………………………………………………………..…S15

Figure S11. Temperature dependence of the in-phase M’ and out-of-phase

susceptibility M’’ (top, right) for Tb2 (TD-3) under an applied dc field of 0.1 T

in a range between 2.0 to 25 K and a variation of frequency, and a zoom in

M’’ to emphasize the shifting maxima………………………………..………S15

Figure S12. Arrhenius fit of Tb2 TD-3…………………………………….……S16

Figure S13. Linear plot of the fitted parameters of 1/2 as a function of T

and as a function of T7, which shows a linear fit in the temperature range

between 3.0-6.0 K, respectively……………………………………………….S16

Figure S14. STM images of the self-assembly of TD-3, TD-5 and the free-

base porphyrins 7a, 7b at the 1-phenyloctane/HOPG interface…………...S17

Equation 1 and 2 for simultaneous fits of M’ and M’’……………………….S17

Resulting parameters of and with CC-Fit of Tb2 TD-3…………………...S18

Resulting parameters of and for simultaneous fits of M’ and M’’ by a

least-squares fitting of the data to a generalized Debye model for two

relaxation processes for Tb2 TD-3 …………….…………………………..….S19

3. Typical High-Resolution Mass Spectra…………………………………... S20

4. References……………………………………………………………………...S28

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1. Materials, Methods and Instrumentation

General Considerations. All chemicals, unless otherwise noted, were purchased from

commercial sources and were used without further purification. Conventional synthetic

reactions were magnetically stirred under an argon atmosphere while microwave-assisted

reactions were also magnetically stirred and carried out using a Discover SP type

microwave apparatus purchased from the CEM Company. Both types of reactions were

monitored by thin-layer chromatography (TLC) on MERCK silica gel 60 F254 TLC

aluminum sheets. Volatile solvents were removed via reduced distillation using a Büchi

rotary evaporator at the appropriate temperatures and pressures while nonvolatile

solvents such as 1,2,4-trichlorobenzene (TCB) and ortho-dichlorobenzene (DCB) were

removed by reduced pressure distillation using a vacuum pump at the appropriate

temperatures and pressures. Flash column chromatography was performed on Merck

silica gel 60 (0.040-0.063 µm). UV-vis and UV-vis-NIR measurements in CHCl3 were

performed on a JASCO V-670 UV-vis-NIR spectrometer equipped with a Peltier sample

holder. Mass spectrometry analysis were performed at the Spectropole (the analytical

facilities of Aix-Marseille University) with a Waters SYNAPT G2 HDMS

quadrupole/Time of flight (QTOF) mass spectrometer (Manchester, UK). Samples were

diluted in a methanolic solution supplemented with 3 mM ammonium acetate as an

ionization salt and directly analyzed by electrospray ionization operated in the positive

ion mode.

Electrochemical and Spectroelectrochemical Measurements. Benzonitrile (PhCN)

was purchased from Sigma-Aldrich Co. and freshly distilled over P2O5 before use.

Tetra-n-butyl- ammonium perchlorate (TBAP) was purchased from Sigma-Aldrich Co.

(Caution! Perchlorate salts are potentially explosive and should be handled with care.)

All electrochemical and spectro-electrochemical experiments were performed in

oven-dried glassware under a slight positive pressure of argon. Cyclic voltammetry was

performed at 298 K using EG&G Princeton Applied Research (PAR) 173

potentiostat/galvanostat. A homemade three-electrode cell was used for cyclic

voltammetric measurements and consisted of a glassy carbon working electrode, a

platinum counter electrode and a homemade saturated calomel reference electrode (SCE).

The SCE was separated from the bulk of the solution by a fritted glass bridge of low

porosity, which contained the solvent/supporting electrolyte mixture. UV−vis spectra of

the neutral compounds were measured with a Hewlett-Packard 8453 diode array

spectrophotometer. Thin-layer UV−vis spectroelectrochemical experiments were

performed using a home-built thin-layer cell, which has a transparent platinum-net

working electrode. Potentials were applied and monitored with an EG&G PAR Model

173 potentiostat. High-purity N2 from Trigas was used to deoxygenate the solution and

N2 was kept over the solution during each electrochemical and spectroelectrochemical

experiment.

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Magnetic Measurements. Magnetic susceptibility data were obtained using a Quantum

Design SQUID magnetometer MPMS-XL operating between 1.8 and 300 K. DC

measurements were performed on a polycrystalline sample of 17.1 mg Tb2 (TD-3) and

8.1 mg Dy2 (TD-4) and. The sample was wrapped in a polyethylene membrane and

subjected to fields in a range from 0 to 7 T. The magnetization data was collected at 100

K in order to check for ferromagnetic impurities that were found to be absent in the

sample. Diamagnetic corrections were applied to correct for contributions from the

sample holder, and the inherent diamagnetism of the sample was estimated with the use

of Pascal’s constants. AC measurements were carried out with frequencies between 1 to

1500 Hz.

Scanning Tunneling Microscope (STM) measurements. The corresponding triple-

decker complexes were dissolved in 1-phenyloctane and drop-cast deposited onto freshly

cleaved (highly oriented pyrolytic graphite) HOPG (Goodfellow). STM observation was

performed by using low-current STM (Bruker MultiMode 8 with Nanoscope V

Controller) at the solid/liquid interface at room temperature. A mechanically cut Pt/Ir

(80:20) wire was used as the STM tip. Images were processed using WSxM software.1

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2. Experimental Data

Synthetic Procedures

Compounds 4-(2,5,5-trimethyl-1,3-dioxan-2-yl) phthalonitrile 5,2 free-base meso-

di-/tetra-undecylporphyrins 7a/7b and meso-tetra-hexadecylporphyrin 7c3 were prepared

according to published procedures.

Synthesis of lanthanide double-decker complexes 6ac:

Double-decker 6a: in a typical procedure following one published literature,4 under an

argon atmosphere, a mixture of 5 (300 mg, 1.17 mmol), DBU (91 mg, 0.60 mmol) and

Gd(acac)3·2H2O (32 mg, 0.07 mmol) was heated in amyl alcohol (5 mL) under reflux

overnight to give a dark greenish-blue solution. The volatiles were removed in vacuum

after which the residue was chromatographed with CHC13/CH3OH (40:1) as eluent. The

first green band contained a small amount of the metal-free phthalocyanine as determined

by UV-vis spectrometry. A following dark greenish-blue band contained the sandwich

compound and was collected and evaporated under reduced pressure. The obtained crude

product was further purified by the same chromatographic procedure to yield a dark blue

powder 6a (290 mg, 90%). Rf = 0.51 (CHC13/CH3OH, 40/1). UV-vis-NIR (CHCl3):

(nm) = 325, 461.5, 609.5, 677, 908 (br.), 1659 (br.). ESI-HR-MS: M+2H2+

= 1104.4574;

calcd. for M+ 2H = C120H130N16 O16 Gd2+

=1104.4555.

Double-decker 6b: the dark blue powder 6b was prepared as discussed above for 6a

from 5 (200 mg, 0.78 mmol), DBU (61 mg, 0.40 mmol) and Tb(acac)3·nH2O (23 mg,

0.05 mmol). Yield: 175 mg, 81%. Rf = 0.48 (CHCl3/CH3OH, 40/1). UV-vis-NIR (CHCl3):

(nm) = 325, 458, 608.5, 676.5, 918 (br.), 1619 (br.). ESI-HR-MS: M+2H2+

=1105.4562; calcd. for M+2H = C120H130N16O16Tb2+

=1105.4558.

Double-decker 6c: the dark blue powder 6c was also prepared as discussed above for 6a

from 5 (200 mg, 0.78 mmol), DBU (61 mg, 0.40 mmol) and Dy(acac)3·nH2O (23 mg,

0.05 mmol). Yield: 120 mg, 56%. Rf = 0.64 (CHCl3/CH3OH, 40/1). UV-vis-NIR (CHCl3):

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(nm) = 324.5, 462.5, 607, 674, 920 (br.), 1587 (br.). ESI-HR-MS: M+2H2+

=1107.4594; calcd. for M+2H = C120H130N16O16Dy2+

=1107.4579.

Synthesis of lanthanide triple-decker complexes TD-15:

Synthesis of triple-decker TD-1:

Conventional procedure according to published literature.5 A mixture of meso-p-

diundecylporphyrin 7a (31 mg, 0.05 mmol) and Gd(acac)3·2H2O (136 mg, 0.3 mmol) in

1,2,4-trichlorobenzene (6 mL) was heated to reflux in a sea sand bath at 230 ℃ and

stirred for 4 h. The resulting cherry red solution which contained the (Por)Gd(acac)

half-sandwich complex was cooled to room temperature and then the double decker 6a

(110 mg, 0.05 mmol) was added. The mixture was refluxed for 8h (or even longer to 20

h). After removing the solvent under reduced pressure distillation, the sample was

directly sent for mass spectra. The result (Figure S2) showed only a very weak ion peak

attributed to the target TD-1 while the ion peaks of the starting double-decker 6a

dominated, proving that the reaction indeed did occur but that only trace amounts of the

desired product were obtained.

Optimized microwave-assisted procedure. A mixture of meso-p-diundecylporphyrin 7a

(19 mg, 0.03 mmol) and Gd(acac)3·2H2O (84 mg, 0.18 mmol) in ortho- dichlorobenzene

(3 mL) were poured into a 10 mL vial with a pressure cap under 180 ℃, 10 min, 10 bar,

150 W (power), off (powerMax), stirring (high). After cooling down to room temperature,

the double-decker 6a (66 mg, 0.03 mmol) was added and was subjected to 220 ℃, 30

min, 17 bar, 250 W (power), off (powerMax), stirring (high). The solvent was then

removed and the residue was chromatographed with CHCl3/CH3OH (50:1). The first

band (purple, PorH2) was not collected. The second band (green) was collected and

chromatographed with CHCl3 which afforded a green oily powder (34 mg, 38%). Rf =

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0.61 (CHC13/CH3OH, 50/1). UV-vis (CHCl3): (nm) = 340.5, 400, 506, 580, 620.5,

727.5. ESI-HR-MS: M+2H2+

= 1491.6437; calcd. for the maximum isotope of

M+2H2+

= C162H186N20O16Gd22+

= 1491.6437.

Synthesis of triple-decker TD-2: Attempts was also made to prepare TD-2 under the

conventional conditions as for TD-1, but the low-resolution mass spectrum shown in

Figure S3, gave only very weak ion peaks which could be attributed to the target TD-2

while the ion peaks from the starting double-decker 6a were again totally dominant. Thus

the microwave-assisted synthesis of TD-2 was carried out as for TD-1 from

meso-tetraundecylporphyrin 7b (19 mg, 0.02 mmol), Gd(acac)3·2H2O (55 mg, 0.12

mmol) and the double decker 6a (44 mg, 0.02 mmol) giving a dark green oily powder

TD-2. Yield: 22 mg, 33%. Rf = 0.82 (CHCl3/CH3OH, 50/1). UV-vis (CHCl3): (nm) =

343, 406, 507, 579, 630.5, 735. ESI-HR-MS: M+2H2+

= 1645.8159; calcd. for the

maximum isotope of M+2H2+

= C184H230N20O16Gd22+

= 1645.8161.

Synthesis of triple-decker TD-3: the dark green oily powder TD-3 was also prepared

under microwave-assisted condition as for TD-1 from meso-tetraundecylporphyrin 7b

(57 mg, 0.06 mmol), Tb (acac)3·nH2O (164 mg, 0.36 mmol) and double-decker 6b (130

mg, 0.06 mmol). Yield: 55 mg, 28%. Rf = 0.77 (CHCl3/CH3OH, 50/1). UV-vis (CHCl3):

(nm) = 342.5, 407, 508, 581, 631, 742. ESI-HR–MS: M+2H2+

= 1647.8182; calcd.

for the maximum isotope of M+2H2+

= C184H230N20O16Tb22+

= 1647.8179.


under microwave-assisted condition as for TD-1 from meso-tetraundecylporphyrin 7b

(37 mg, 0.04 mmol), Dy(acac)3·nH2O (110 mg, 0.24 mmol) and double decker 6c (80 mg,

0.04 mmol). Yield: 65 mg, 36%. Rf = 0.85 (CHCl3/CH3OH, 50/1). UV-vis (CHCl3):

(nm) = 343.5, 418, 511, 584, 634, 749. ESI-HR-MS M+2H2+

=1651.3202; calcd. for

the maximum isotope of M+2H2+

= C184H230N20O16Dy22+

= 1651.3203.


under microwave-assisted condition as for TD-1 from meso-tetrahexadecylporphyrin 7c

(18 mg, 0.015 mmol), Tb (acac)3·nH2O (41 mg, 0.09 mmol) and double-decker 6b (33

mg, 0.015 mmol). Yield: 12 mg, 22%. Rf = 0.93 (CHC13/CH3OH, 50/1). UV-vis (CHCl3):

(nm) = 341, 407, 509, 581, 631, 741. ESI-HR–MS: M+2H2+

= 1787.9751; calcd. for

the maximum isotope of M+2H2+

= C204H270N20O16Tb22+

= 1787.9744.

S8

Figure S1. UV-vis-Near-Infrared absorption spectra of the double-decker complexes

6ac.

S9

Figure S2. ESI-MS spectrum of triple-decker TD-1 obtained following the conventional

Weiss procedure.5 Therein, very weak ion peaks centered at M+2H

2+ = 1491.7 could be

attributed to the target TD-1 (calcd. for M+2H]2+

= C162H186N20O16Gd22+

=1491.6437).

The dominant ion peaks centered at M’+2H2+

= 1105.0, M’+H+

= 2208.9 could be

attributed to the starting double decker 6a (calcd. for M+2H]2+

= C120H130N16O16Gd2+

=1104.4555).

Figure S3. ESI-MS mass spectrum of triple-decker TD-2 obtained following the

conventional Weiss procedure.5 Therein, very weak ion peaks centered at M+2H

2+ =

1646.3, M+H+ = 3291.6 could be attributed to the target TD-2 (calcd. for M+2H

2+ =

C184H230N20 O16Gd22+

=1645.8161.). The dominant ion peaks centered at 2208.9 could be

attributed to the starting double-decker 6a (calcd. for M+2H = C120H130N16 O16Gd2+

=1104.4555).

m/z1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800 2900

%

0

100

STB-HG-036-01_D1AA_DP80 4 (0.086) Cm (2:9) TOF MS ES+ 1.47e5

1105.0

[M+2H]2+

[M’+H]+

2208.9

1491.72827.0

[M’+2H]2+

m/z1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800 2900 3000 3100 3200 3300

%

0

100

STB-HG-037-05_D1AA_CONE150 22 (0.393) Cm (1:22) TOF MS ES+1.27e5

2208.9

1109.5

1282.6

1369.7

1646.3

3291.6

2223.9

1023

.510

79.5

1191

.611

96.6

[M+H]+

[M+2H]2+

m/z3270 3272 3274 3276 3278 3280 3282 3284 3286 3288 3290 3292 3294 3296 3298 3300 3302 3304 3306 3308 3310 3312 3314

3291.6

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Figure S4. UV-vis absorption spectra of the triple-decker complexes TD-1TD-5 in

PhCN (c = 8.5×10-6

mol/L).

Figure S5. Normalized UV-vis-NIR absorption spectra of the triple-decker complexes

TD-1TD-4 in CHCl3. After enlargement of the NIR range spectra (1000 – 1400 nm)

(inset), very weak and characteristic absorption bands of these triple-decker complexes

could be observed, this is similar to the reported (Por)Ln(Pc)Ln(Por)-type triple-decker

complexes.6

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Figure S6. Normalized UV-vis absorption spectra of Por-7a and Por-7b in CHCl3.

S12

Figure S7. UV-vis spectral changes of TD-1 during controlled potential (a) 1st oxidation

at 0.70 V and (b) 1st reduction at -0.90 V in PhCN containing 0.1 M TBAP.

S13



S14



S15

Figure S10. Out-of-phase susceptibility of DyIII

triple-decker (TD-4) (left) and TbIII

triple-decker (TD-3) (right) at varying field.

Figure S11. Temperature dependence of the in-phase M’ (top, left) and out-of-phase

susceptibility M’’ (top, right) for Tb2 (TD-3) under an applied dc field of 0.1 T in a

range between 2.0 to 25 K and a variation of frequency, and a zoom in M’’ (bottom) to

emphasize the shifting maxima.

S16

Figure S12. Arrhenius fit of Tb2 TD-3, giving Ueff,1 = 5.7 K and 0 = 5.12.10

-3 s (R =

0.999, pink circles) fitted in the whole temperature range and Ueff,2 = 12.4 K and 0 =

5.41.10

-6 s (R = 0.998, purple squares) fitted between 3.0 and 6.0 K (over the whole

temperature range, see right picture, gives slightly different values).

Figure S13. Linear plot of the fitted parameters of 1/2 as a function of T (left) and as a

function of T7 (right), showing a linear fit in a temperature range between 3.0-6.0 K,

respectively, which conforms to 1/ ∝ T7, proving that this temperature region is

dominated by a Raman process.

S17

Figure S14: STM images of the self-assembly of triple-deckers and free-base porphyrins

at the 1-phenyloctane/HOPG interface. A: TD-3 (tunneling current I = 3 pA, sample bias

-1550 mV); B: TD-5 (I = 6 pA, sample bias -500 mV); C: Por-7b (I = 5 pA, sample bias

800 mV). D: Por-7c (I = 10 pA, sample bias 500 mV)

Equation 1 and 2 for simultaneous fits of M’ and M’’:

(𝟏) 𝜒′(𝜔)

= 𝜒𝑆,𝑡𝑜𝑡 + 𝛥𝜒1 1 + (𝜔𝜏1)1−𝛼1 sin (

𝜋𝛼12 )

1 + (𝜔𝜏1)1−𝛼1 sin (𝜋𝛼1

2 ) + (𝜔𝜏1)(2−2𝛼1)

+ 𝛥𝜒2

1 + (𝜔𝜏2)1−𝛼2 sin (𝜋𝛼2

2 )

1 + (𝜔𝜏2)1−𝛼2 sin (𝜋𝛼2

2 ) + (𝜔𝜏2)(2−2𝛼2)

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(𝟐) 𝜒′′(𝜔) = 𝛥𝜒1 1 + (𝜔𝜏1)1−𝛼1 cos (

𝜋𝛼12 )

1 + (𝜔𝜏1)1−𝛼1 sin (𝜋𝛼1

2 ) + (𝜔𝜏1)(2−2𝛼1)

+ 𝛥𝜒2

1 + (𝜔𝜏2)1−𝛼2 cos (𝜋𝛼2

2 )

1 + (𝜔𝜏2)1−𝛼2 sin (𝜋𝛼2

2 ) + (𝜔𝜏2)(2−2𝛼2)

Resulting parameters of and with CC-Fit of Tb2 (TD-3):

##################################################

########## CC-FIT ##########

########## ##########

########## (C) 2014 ##########

########## NICHOLAS F CHILTON ##########

########## ##########

########## [email protected] ##########

##################################################

Number of relaxation processes: 1

Number of temperatures: 11

Number of frequencies: 20

ChiS ChiT Tau Alpha Residual

0.763592E+00 0.134241E+02 0.175727E+00 0.494238E+00 0.190617E+00

0.124458E+01 0.984604E+01 0.717742E-01 0.443291E+00 0.189188E+00

0.148706E+01 0.776440E+01 0.424778E-01 0.397138E+00 0.133435E+00

0.156931E+01 0.639790E+01 0.301643E-01 0.359401E+00 0.904576E-01

0.156316E+01 0.542021E+01 0.236851E-01 0.332623E+00 0.565208E-01

0.150605E+01 0.469898E+01 0.199593E-01 0.315856E+00 0.496655E-01

0.144999E+01 0.412337E+01 0.167974E-01 0.293592E+00 0.269924E-01

0.136914E+01 0.367084E+01 0.147514E-01 0.281555E+00 0.208525E-01

0.130268E+01 0.330105E+01 0.132828E-01 0.268128E+00 0.141159E-01

0.123823E+01 0.299001E+01 0.119604E-01 0.255567E+00 0.116974E-01

0.116843E+01 0.273555E+01 0.108661E-01 0.251895E+00 0.817031E-02

S19

Resulting parameters of andfor simultaneous fits of M’

and M’’ using a

least-squares fitting of the data to a generalized Debye model for two relaxation

processes for Tb2 (TD-3):

temp 1.8 K 2.2 K 2.6 K 3.0 K

parameter value std. dev. value std. dev. value std. dev. value std. dev.

d1 7.60116 0.27262 5.55819 0.20974 4.46964 0.11418 3.66734 0.08908

1 0.11589 0.00187 0.06933 0.00105 0.04724 5.56E-04 0.03507 4.39E-04

1 0.27682 0.01271 0.24957 0.01138 0.24264 0.00784 0.23262 0.00776

d2 2.40254 0.21478 2.62299 0.22934 2.39391 0.1601 2.24024 0.17399

2 0.00232 3.67E-04 0.0011 1.74E-04 4.45E-04 3.41E-05 2.02E-04 1.55E-05

2 0.43728 0.02119 0.49145 0.02725 0.49156 0.02579 0.48464 0.03213

S,tot 0.36817 0.02635 0.32736 0.05133 0.26424 0.06175 0.1452 0.09777

temp 3.5 K 3.9 K 4.4 K 4.7 K

parameter value std. dev. value std. dev. value std. dev. value std. dev.

d1 3.26597 0.05451 2.72751 0.07675 2.30689 0.04059 1.95481 0.03341

1 0.02686 3.88E-04 0.02293 5.36E-04 0.01935 2.88E-04 0.01729 2.14E-04

1 0.24642 0.00744 0.23838 0.01156 0.22165 0.00731 0.20821 0.00613

d2 1.4269 0.09454 1.42029 0.18278 1.31317 0.12072 1.32481 0.11916

2 1.88E-04 1.22E-05 1.26E-04 2.08E-05 9.94E-05 1.34E-05 7.98E-05 1.21E-05

2 0.3251 0.03239 0.36087 0.05833 0.35077 0.0401 0.40034 0.03621

S,tot 0.54253 0.058 0.42743 0.12758 0.41644 0.09126 0.32297 0.09226

temp 5.1 K 5.5 K 6.0 K

parameter value std. dev. value std. dev. value std. dev.

d1 1.75043 0.03256 1.55151 0.03341 1.39415 0.02914

1 0.01524 2.28E-04 0.01362 2.33E-04 0.0124 2.17E-04

1 0.20863 0.00713 0.20346 0.00806 0.20293 0.00789

d2 1.18822 0.14298 1.15368 0.18845 0.96558 0.14414

2 6.39E-05 1.38E-05 4.88E-05 1.56E-05 5.66E-05 1.52E-05

2 0.36951 0.04609 0.37331 0.05701 0.35022 0.05567

S,tot 0.31569 0.11777 0.25142 0.16209 0.34901 0.12139

S20

3. Typical High-Resolution Mass Spectra

Double-decker 6a:

m/z error (mDa) error (ppm)

calculated value 1105.4569 - -

1 1105.4590 + 2.1 + 1.9

experimental value 2 1105.4583 + 1.4 + 1.3

3 1105.4589 + 2.0 + 1.8

These experimental determined values are associated with an ion of elementary

composition C120H130N16O16Gd2+

.

Accurate mass measurements obtained for the isotopic peak detected at m/z 1105.5 after

electrospray ionization operated in positive ion mode putting into evidence from the

sample, the ion [M+2H]2+

.

ESI-MS spectrum acquired in the positive mode of electrospray ionization of the sample

6a. The targeted ion are detected at m/z 1104.4574, m/z 1104.9584, m/z 1105.4583 (violet

line) while the peaks retained for internal calibration are observed at m/z 1069.5922 and

m/z1070 1075 1080 1085 1090 1095 1100 1105 1110 1115 1120 1125

%

0

100

STB-HG-032-02-04_D2AA_CONE50_MEX2_copy 10 (0.188) AM2 (Ar,18000.0,0.00,0.00); Cm (1:10) TOF MS ES+ 3.07e5

1104.9584

1069.59221119.6184

1104.45741105.4583

S21

m/z 1119.6184 (green rectangles).

Double-decker 6b:

ESI-MS spectrum of the sample 6b acquired in the positive mode of electrospray

ionization.



1 1105.4558 - 0.4 - 0.4

experiment value 2 1105.4567 + 0.5 + 0.5

3 1105.4567 + 0.5 + 0.5


composition C120H130N16O16Tb2+

.

Accurate mass measurements obtained for the maximum isotopic detected at m/z 1105.5

after electrospray ionization operated in positive ion mode putting into evidence the ion

[M+2H]2+

in positive mode from the sample.

m/z1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250

%

0

100


1105.5

2209.7[M+H]+

[M+2H]2+

m/z1070 1075 1080 1085 1090 1095 1100 1105 1110 1115 1120

%

0

100

STB-HG-038-02_D2AA_CONE40_MEX1_copy 9 (0.170) AM2 (Ar,18000.0,0.00,0.00); Cm (1:10) TOF MS ES+2.74e5

1105.4558

1069.5922

1119.6184

S22

ESI-MS Spectrum acquired in the positive mode of electrospray ionization of the sample

6b. The targeted ion is detected at m/z 1105.4558 (blue rectangle) while the peaks

retained for internal calibration are observed at m/z 1069.5922 and m/z 1119.6184 (violet

ellipses).

Double-decker 6c:

ESI-MS spectrum of the sample 6c acquired in the positive mode of electrospray

ionization.



1 1107.4598 + 1.9 + 1.7


3 1107.4594 + 1.5 + 1.4

These experimental determined values are associated with an ion of

elementary composition C120H130N16O16Dy2+

.



[M+2H]2+


m/z1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800 2900 3000 3100 3200 3300 3400

%

0

100


2212.9

1107.5

Figure 2

[M+2H]2+

M+●

m/z1015 1020 1025 1030 1035 1040 1045 1050 1055 1060 1065 1070 1075 1080 1085 1090 1095 1100 1105 1110 1115 1120 1125 1130 1135

%

0

100


1107.4594

1020.5738

1120.6262

S23

ESI-MS Spectrum of the sample 6c acquired in the positive mode of electrospray

ionization and calibrated for the targeted value. The targeted ion is detected at m/z

1107.4594 (blue rectangle) while the peaks retained for internal calibration are observed

at m/z 1020.5738 and m/z 1120.6262 (violet ellipses).

TD-1:

ESI-MS Mass Spectrum of the sample TD-1 acquired in the positive mode of

electrospray ionization. The targeted ion is detected at m/z 1491.6437.



1 1491.6453 + 1.6 + 1.1


3 1491.6437 0 0



.



[M+2H]2+


m/z1480 1482 1484 1486 1488 1490 1492 1494 1496 1498 1500 1502 1504 1506

%

0

100

STB-HG-036-02_D1IPAA_CONE150_MEX3 1 (0.034) AM2 (Ar,18000.0,0.00,0.00); Cm (1:57) TOF MS ES+ 1.34e5

1491.6437 [M+2H]2+

S24

TD-2:



1 1645.8159 - 0.2 - 0.1

experimental value 2 1645.8157 - 0.4 - 0.2

3 1645.8171 + 1.0 + 0.6



.


after electrospray ionization operated in positive ion mode from the sample by

electrospray ionization putting into evidence the ion [M+2H]2+

in positive mode.


electrospray ionization. The targeted ion is detected at m/z 1645.8159 (blue rectangle)

while the peaks retained for internal calibration are observed at m/z 1620.8883 and m/z

1720.9408 (violet ellipses).

m/z1615 1620 1625 1630 1635 1640 1645 1650 1655 1660 1665 1670 1675 1680 1685 1690 1695 1700 1705 1710 1715 1720 1725 1730 1735

%

0

100


1620.8883

1720.9408

1645.8159

S25

TD-3:



1 1647.8193 + 1.4 + 0.8


3 1647.8187 + 0.8 + 0.5



.




in positive mode.

ESI-MS spectrum of the sample TD-3 acquired in the positive mode of electrospray

ionization. The targeted ion is detected at m/z 1647.8182 (blue rectangle) while the peaks

retained for internal calibration are observed at m/z 1620.8883 and m/z 1720.9408 (violet

ellipses).

m/z1615 1620 1625 1630 1635 1640 1645 1650 1655 1660 1665 1670 1675 1680 1685 1690 1695 1700 1705 1710 1715 1720 1725

%

0

100


1620.8883

1647.8182

1720.9408

S26

TD-4:



1 1651.3202 - 0.1 - 0.1


3 1651.3208 + 0.5 + 0.3


composition C184H230N20O16Dy22+

.




in positive mode.

ESI-MS spectrum of the sample TD-4 acquired in the positive mode of electrospray

ionization. The targeted ion is detected at m/z 1651.3202 (blue rectangles) while the

peaks retained for internal calibration are observed at m/z 1620.8882 and m/z 1720.9408

(violet ellipses).

m/z1615 1620 1625 1630 1635 1640 1645 1650 1655 1660 1665 1670 1675 1680 1685 1690 1695 1700 1705 1710 1715 1720 1725 1730 1735

%

0

100

STB-HG-041-01_D1AA_CONE100_DG1200_MEX1_copy 23 (0.410) AM2 (Ar,18000.0,0.00,0.00); Cm (1:57) TOF MS ES+4.93e5

1620.8882

1720.9408

1651.3202

S27

TD-5:


electrospray ionization. The targeted ion is detected at m/z 1787.9751.

m/z error(mDa) error (ppm)


1 1787.9751 + 0.7 + 0.4

Experimental value 2 1787.9775 + 3.1 + 1.7

3 1787.9785 + 4.1 + 2.3



.



[M+2H]2+

in positive mode.

[M+2H]2+

m/z1755 1760 1765 1770 1775 1780 1785 1790 1795 1800 1805 1810 1815 1820 1825 1830

%

0

100

STB-HG-042_D1AA_CONE150_MEX1 10 (0.188) AM2 (Ar,18000.0,0.00,0.00); Cm (1:10) TOF MS ES+ 2.26e5

1787.9751

S28

4. References

(1) Horcas, I.; Fernández, R.; Gomez-Rodriguez, J.; Colchero, J.; Gómez-Herrero, J.;

Baro, A. “WSXM: A Software for Scanning Probe Microscopy and A Tool for

Nanotechnology” Rev. Sci. Instrum. 2007, 78, 013705.

(2) Jin, H.-G.; Balaban, M. C.; Chevallier-Michaud, S.; Righezza, M.; Balaban, T. S.

“Biomimetic Self-assembling Acylphthalocyanines” Chem. Commun. 2015, 51,

11884-11887.

(3) Plamont, R.; Kikkawa, Y.; Takahashi, M.; Kanesato, M.; Giorgi, M.; Chan Kam Shun,

A.; Roussel, C.; Balaban, T. S. “Nanoscopic Imaging of meso-Tetraalkylporphyrins

Prepared in High Yields Enabled by Montmorrilonite K10 and 3 Å Molecular Sieves”

Chem. Eur. J. 2013, 19, 11293-11300.

(4) Jiang, J.; Liu, R. C.; Mak, T. C.; Chan, T. D.; Ng, D. K. “Sandwith FET Containing

Organic Semiconductor and Its Preparing Process” Polyhedron 1997, 16, 515-520.

(5) Chabach, D.; De Cian, A.; Fischer, J.; Weiss, R.; Bibout, M. E. M. “Mixed-metal

Triple-decker Sandwich Complexes with the Porphyrin/Phthalocyanine/Porphyrin Ligand

System” Angew. Chem. Int. Ed. 1996, 35, 898-899.

(6) Birin, K. P., Gorbunova, Y. G., Tsivadze, A. Y. “Early Lanthanides

(Porphyrinato)(Crownphthalocyaninates): Efficient Synthesis and NIR Absorption

Characteristics” Macroheterocycles 2010, 3, 210-217.

microwave-mediated synthesis of bulky lanthanide porphyrin ... · microwave-mediated synthesis of...

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