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Supporting Information

for

Synthesis and characterization of ML and ML2 metal complexes with amino acid substituted bis(2-picolyl)amine ligands.

Đani Škalamera,a Ernest Sanders,a Robert Vianello,a Aleksandra Maršavelski,a Andrej

Pevec,b Iztok Turelb and Srećko I. Kirin*,a a Ruđer Bošković Institute, Bijenička cesta 54, 10 000 Zagreb, Croatia. E-mail: [email protected] b Faculty of Chemistry and Chemical Technology, University of Ljubljana, Vecna pot 113, 1000 Ljubljana, Slovenia.

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2015

S2

Table of contents: 1. NMR spectra of ligands L1‐L5 ...................................................................................... S3‐S15

2. MS spectra of ligands L1‐L5 ....................................................................................... S16‐S20

3. NMR spectra of ML complexes ................................................................................. S21‐S35

4. NMR spectra of complex 12Zn ................................................................................... S36‐S41

5. IR spectra of metal complexes ......................................................................................... S42

6. X‐ray single crystal structure of coordination polymer 2p ............................................... S51

7. Crystallographic numbering scheme ................................................................................ S52

S3

1. N

MR spectra of ligands L1‐L5.

1H NMR (300 M

Hz, CD3CN) of ligand L1. B

pa‐CH2‐CH2‐CO

2Me.

PPM

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0.0

pp

,;

S4

1H NMR (600 M

Hz, DMSO

‐d6) of ligand L1. B

pa‐CH2‐CH2‐CO

2Me.

9.00308.48288.48168.48038.47878.47498.47368.47218.47087.78077.77777.76797.76507.75527.75237.47247.45937.25847.25687.25027.24857.24607.24427.23797.2362

3.7450

3.5409

3.3130

2.77302.76122.74952.55522.54362.53182.50892.50592.50292.49992.4969

0.0000

S5

13C NMR (75 M


pa‐CH2‐CH2‐CO

2Me.

S6

1H NMR (600 M

Hz, CDCl 3) of ligand L2. B

pa‐CH2‐CO

2Me.

PPM

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0.0

pj

S7

1H NMR (300 M


pa‐CH2‐CO

2Me.

S8

13C NMR (75 M


pa‐CH2‐CO

2Me.

S9

1H NMR (300 M

Hz, CDCl 3) of ligand L3. B

qa‐CH2‐CO

2Me.

S10

1H NMR (300 M


qa‐CH2‐CO

2Me.

S11

13C NMR (75 M


qa‐CH2‐CO

2Me.

S12

1H NMR (300 M


pa‐CH(CH3)Ph.

S13

13C NMR (75 M


pa‐CH(CH3)Ph.

S14

1H NMR (300 M

Hz, DMSO


qa‐CH(CH3)Nph.

S15

13C NMR (75 M

Hz, DMSO


qa‐CH(CH3)Nph.

PPM

160

150

140

130

120

110

100

9080

7060

5040

3020

S16

2. M

S spectra of ligands L1 ‐ L5.

MS of ligand L1. B

pa‐CH2‐CH2‐CO

2Me.

2

x10

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.91

+ S

can:

1 (0

.174

-0.4

90 m

in, 2

2 sc

ans)

es_

2_20

1409

29_t

ic.d

286.

3000

0

308.

3000

0

Cou

nts

(%) v

s. M

ass-

to-C

harg

e (m

/z)

2040

6080

100

120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420

440

460

480

S17

MS of L2. B

pa‐CH2‐CO

2Me

S18

MS of ligand L3. B

qa‐CH2‐CO

2Me.

S19

MS of ligand L4. B

pa‐CH(CH3)Ph.

2x1

0

00.

050.1

0.150.

20.

250.3

0.350.

40.

450.5

0.550.

60.

650.7

0.750.

80.

850.9

0.951

+ S

can

(0.1

93-0

.446

min

, 35

scan

s) E

S_6

_201

4042

5_T

IC.d 20

0.30

000

304.

4000

0

105.

3000

0

326.

3000

0

Cou

nts

(%) v

s. M

ass-

to-C

harg

e (m

/z)

2040

6080

100

120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420

440

460

480

S20

MS of ligand L5. Bqa‐CH(CH3)Nph.

2

x10

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.91

+ S

can:

1 (0

.144

-0.4

45 m

in, 2

1 sc

ans)

ES

_40_

2015

0217

_TIC

.d

454.

3000

0

300.

2000

015

5.20

000

Cou

nts

(%) v

s. M

ass-

to-C

harg

e (m

/z)

2040

6080

100

120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420

440

460

480

500

520

540

560

580

S21

3. N

MR spectra of ML complexes.

1H NMR (600 M

Hz, CD3CN) of complex 1n. [Zn

(L1)(NO

3) 2].

S22

13C NMR (75 M


(L1)(NO

3) 2].

S23

1H NMR (600 M

Hz, DMSO

‐d6) of complex 1n. [Zn

(L1)(NO

3) 2].

S24

1H NMR (600 M

Hz, CD3CN) of complex 1b. [Zn

(L1)Br 2].

S25

1H NMR (600 M

Hz, CD3CN) at ‐40 °C of complex 1b. [Zn

(L1)Br 2].

S26

13C NMR (75 M

Hz, CD3CN) of complex 1b. [Zn

(L1)Br 2].

PPM

180

160

140

120

100

8060

4020

p[

()

]

172.3862

154.6216

149.2576

141.2455

125.4489124.9198118.2601118.0887118.0482

57.7994

52.295049.0471

29.6709

2.11651.84151.56591.2902

S27

1H NMR (600 M

Hz, DMSO

‐d6) of complex 1b. [Zn

(L1)Br 2].

S28

1H NMR (600 M


(L2)(NO

3) 2].

S29

13C NMR (150 M

Hz, DMSO


(L2)(NO

3) 2].

S30

1H NMR (600 M


(L3)(NO3) 2].

S31

13C NMR (150 M

Hz, DMSO


(L3)(NO

3) 2].

S32

1H NMR (600 M


(L4)(NO3) 2].

S33

13C NMR (150 M

Hz, DMSO


(L4)(NO

3) 2].

S34

1H NMR (300 M

Hz, DMSO


(L5)(NO

3) 2].

1.6110

4.0254

4.8936

8.21588.11397.93297.90357.84547.82117.76737.74057.71587.67887.65317.53387.50917.48447.45257.42787.40627.37957.35377.2930

S35

13C NMR (150 M

Hz, DMSO


(L5)(NO3) 2].

S36

4. N

MR spectra of complex 12Zn

. 1H NMR spectra of complex 12Zn.

1H NMR (300 M

Hz, CD3CN) of complex 12Zn. [Zn

(L1) 2](BF 4) 2.

S37

13C NMR (75 M

Hz, CD3CN) of complex 12Zn. [Zn

(L1) 2](BF 4) 2.

S38

1H NMR (600 M

Hz, CD3CN) at ‐40 C of complex 12Zn

. [Zn

(L1) 2](BF 4) 2.

S39

13C NMR (150 M

Hz, CD3CN) at ‐ 40 C of complex 12Zn

. [Zn

(L1) 2](BF 4) 2.

S40

1H NMR (600 M

Hz, DMSO

‐d6) of complex 12Zn. [Zn

(L1) 2](BF 4) 2.

S41

13C NMR (75 M

Hz, DMSO

‐d6) of complex 12Zn. [Zn

(L1) 2](BF 4) 2.

PPM

160

150

140

130

120

110

100

9080

7060

5040

3020

p[

()]

()

S42

5. IR spectra of metal complexes.

IR (KBr) of complex 1n. [Zn(L1)(NO

3) 2].

S43

IR (KBr) of complex 1b. [Zn(L1)Br 2].

S44


3) 2].

S45


3) 2].

S46


3) 2].

S47


3) 2].

S48

IR (KBr) of complex 12Zn. [Zn(L1) 2](BF 4) 2.

S49

IR (KBr) of complex 12Co. [Co(L1) 2](BF 4) 2.

S50

IR (KBr) of complex 12Ni. [Ni(L1) 2](BF 4) 2.

S51

6. X

‐ray single crystal structure of coordination polymer 2p (tw

o m

onomer units).

S52

7. Crystallographic numbering schem

e, exemplified on complexes 12M and 3n, M

= Zn, Co or Ni.

C3

C2

C1

N1

C5

C4

M1N3

C6

N2

C8

C7

C12

C11

C10

C9

C13

C14

C15O2

O1

C16

axeq

C7

C6

C1

N1

C9

C8

M1N3

C10

N2

C12

C11

C20

C15

C14

C13

C21

C22

C23O2

O1

C24

C2

C5

C4

C3

C19

C18

C16

C17

1 2M

3n

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